CN104678025B - A kind of GC-EI-MS measures the method for fluorine ether bacterium amide residual in fruit and vegerable - Google Patents
A kind of GC-EI-MS measures the method for fluorine ether bacterium amide residual in fruit and vegerable Download PDFInfo
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Abstract
The invention discloses a kind of GC-EI-MS and measure the method for fluorine ether bacterium amide residual in fruit and vegerable, extracting the fluorine ether bacterium amide of residual in sample with acetonitrile or the acetonitrile solution homogenizing containing 1% acetic acid, extracting solution is through primary secondary amine (PSA) and octadecylsilane Bonded Phase (C18) after substrate dispersion purifies, the detection of gas chromatogram-electron impact ion source-mass spectrum (GC-EI-MS), adopt the vehicle solution without pesticide to be measured to set up the standard curve of correction, quantified by external standard method. This method average recovery rate is 93.5%��99.0%, and average relative standard's deviation (RSD) is 3.7%��5.5%, and detection limit, lower than 2.53 �� g/kg, has easy and simple to handle, quick, highly sensitive, reproducible, qualitative, quantitative advantage accurately. " uniform limit " technology requirement of 0.01mg/kg residue limits can be met, for ensureing that our people's food safety, export abroad trade sound development provide strong technical support.
Description
Technical field
The present invention relates to a kind of GC-EI-MS and measure the method for fluorine ether bacterium amide residual in fruit and vegerable, more specifically adopt gas chromatogram-electron impact ion source-mass spectrum (GC-EI-MS) qualitative, quantitative to measure the method for the fluorine ether bacterium amide content of residual in vegetable and fruit, belong to the determination techniques field of persticide residue.
Background technology
Fluorine ether bacterium amide (LH-2010A) is that Shandong United Pesticide Industry Co., Ltd. is in a kind of novel fluorine Benzoylamide series bactericidal agent of innovation synthesis in 2010, chemical name is: N-(3-chloro-5-(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 is much larger than c h bond, hence it is evident that add stability and the physiologically active of organofluorine compound. Fluorinated organic compound has higher fat-soluble and hydrophobicity, it is possible to promote that it absorbs and transmission in vivo, strengthens the binding ability with organism, makes the physiological action of organism change. Fluoro-containing pesticide has such effect equally, and suppression or the toxic action of pathogen or insect are also greatly improved by fluoro-containing pesticide. Find according to the study, fluorine ether bacterium amide is all higher to the virulence of 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 kind of plant pathogen, visible, fluorine ether bacterium amide sterilizes comparatively wide spectrum, can using as a kind of New-type wide-spectrum type antibacterial, development prospect is wide.
Registration, popularization and use along with fluorine ether bacterium amide, about fluorine ether bacterium amide Residue Degradation dynamically and the research of the environmental behaviour such as final residue certainly will increase, simultaneously, if using pesticide not register in this country as the European Union in China's main exit market, Japan and other countries regulation field, when not formulating corresponding residue limits standard, it is exported to the food agricultural product of its country and includes residue limits in the animal derived foods such as livestock meat and all carry out " uniform limit " of 0.01mg/L.
Up to now, have no the report being related in food agricultural product fluorine ether bacterium amide residues detection method both at home and abroad, the gaschromatographic mass spectrometry (GC-EI-MS) in outfit electron impact ionization source is analyzed food Residual Pesticides in Farm Produce tool and is had great advantage, owing to electron impact ionization source mass spectrum is versatility detector, the multi-residue analysis of hundreds of kind pesticide can be realized, can be simultaneously qualitative and quantitative, moderate, therefore existing various testing agencies and enterprise are equipped with gas chromatogram-electron impact ion source-mass spectrograph (GC-EI-MS) and the pesticide residues in food agricultural product are detected, therefore, set up the detection method of fluorine ether bacterium amide residual quantity in gas chromatogram-electron impact ion source-mass spectrum (GC-EI-MS) qualitative and quantitative analysis vegetable and fruit significant.
Summary of the invention
It is an object of the invention to provide a kind of GC-EI-MS and measure the method for fluorine ether bacterium amide residual in fruit and vegerable.
For realizing object above, the technical solution adopted in the present invention is: a kind of GC-EI-MS measures the method for fluorine ether bacterium amide residual in fruit and vegerable, comprises the steps:
(1) extract
Weigh sample in tool plug centrifuge tube, add acetonitrile or the acetonitrile solution homogenizing containing 1% acetic acid extracts 1min, 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 the acetone that volume ratio is 1/1/normal hexane mixed solvent, after crossing film, treat gas chromatogram-electron impact ion source-mass spectrum (GC-EI-MS) detection.
(3) preparation of standard working solution
When the same kind matrix blank sample of not fluorine-containing ether bacterium amide is processed by above-mentioned steps (1), (2), obtain sample extraction and purify residue, add appropriate solvent and mixed standard solution, vortex mixes, and is configured to the fluorine ether bacterium amide series hybrid standard working solution of at least 3 concentration.
(4) gas chromatogram-electron impact ion source-mass spectrography (GC-EI-MS) measures
The standard working solution of each Concentraton gradient in step (3) is carried out GC-EI-MS mensuration, with the chromatographic peak area of standard working solution, its respective concentration is carried out regression analysis, obtain standard working curve; Under the same conditions the sample liquid after purification in step (2) is injected GC-EI-MS to be measured, record the chromatographic peak area of fluorine ether bacterium amide in sample liquid, substitute into standard curve, obtaining fluorine ether bacterium amide content in sample liquid, then the Mass Calculation of sample representated by liquid obtains fluorine ether bacterium amide residual quantity in sample per sample.
Step (1) if in sample dehydrated vegetables and fruit, need to reduce sample weighting amount, and add suitable quantity of water and fully infiltrate.
Step (1) adds sodium chloride during employing acetonitrile extraction saltout, adopt the acetonitrile solution containing 1% acetic acid when extracting, to add sodium acetate and saltout; A certain amount of water need to be added when the sample of moisture content less is saltoutd.
The dispersive solid-phase extraction agent of step (2) mesostroma is by anhydrous magnesium sulfate, C18Form with PSA, anhydrous magnesium sulfate, C in every volume extracting solution18With PSA addition respectively 150mg, 50mg and 25mg.
In step (4), GC conditions is: chromatographic column: HP-5MS capillary chromatographic column, column length 30m, internal diameter 0.25mm, thickness 0.25 ��m; Injector temperature 250 DEG C; Carrier gas: He, not shunt mode sample introduction, sample size: 1 �� L; Constant current mode, flow velocity 1.0mL/min;Heating schedule: initial temperature 60 DEG C keeps 2min, rises to 200 DEG C with the speed of 20 DEG C per minute, then rises to 220 DEG C with the speed of 2 DEG C per minute, then rises to 280 DEG C 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 solvent delay time is 10min, and the ion of monitoring is: 381,382,397,211.
When step (4) measures sample liquid and extraction standard working solution, if sample liquid Pesticides chromatographic peak retention time pesticide retention time corresponding to standard solution is consistent, and in the sample mass spectrum after background correction, selected ion all occurs, and abundance of ions is more consistent than the abundance of ions ratio with standard solution, then can determine whether sample liquid exists this pesticide; If above-mentioned two condition can not meet simultaneously, then judge without this kind of pesticide.
The beneficial effects of the present invention is:
The present invention utilizes dispersive solid-phase extraction technology, establish simplicity, quickly and the sample-pretreating method of sample mesostroma interference can be prevented effectively from, this pre-treating method is applied in conjunction with GC-EI-MS the qualitative confirmation of fluorine ether bacterium amide and detection by quantitative in vegetable and fruit, average recovery rate is 93.5%��99.0%, average relative standard's deviation (RSD) is 3.7%��5.5%, detection limit, lower than 2.53 �� g/kg, has easy and simple to handle, quick, accurate, highly sensitive and reproducible advantage. " uniform limit " technology requirement of 0.01mg/kg residue limits can be met, for ensureing that our people's food safety, export abroad trade sound development provide strong technical support.
Accompanying drawing explanation
Fig. 1 is the selection chromatography of ions figure of the 100ng/mL fluorine ether bacterium amide mark liquid being added in blank Fructus Mali pumilae substrate.
Fig. 2 is the selection chromatography of ions figure of the Fructus Mali pumilae blank sample of not fluorine-containing ether bacterium amide.
The fluorine ether bacterium amide standard working curve that Fig. 3 is is substrate preparation with the Fructus Mali pumilae blank sample of not fluorine-containing ether bacterium amide.
Detailed description of the invention
Now with following embodiment, the present invention is described, but is not restriction the scope of the present invention.
The instrument used in embodiment and reagent
T18Basic homogenizer (IKA, Germany); 5810R centrifuge (Eppendorf, Germany); MS3 basic model vortex mixer (IKA, Germany); 7890N gas chromatogram-5977C mass spectrograph (Agilent, USA); Primary secondary amine (PSA) adsorbent (40��60 ��m), octadecylsilane Bonded Phase (C18) cleanser (40��60 ��m) 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 analytical pure, 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 amide residual quantity in Fructus Mali pumilae
(1) sample pre-treatments
Weighing the Fructus Mali pumilae 10.0g through fully mixing in 50mL centrifuge tube, accurately add 20mL acetonitrile, homogenizing extracts 1min, adds 3g anhydrous magnesium sulfate and 2g sodium chloride, and after vortex 1min, 7000r/min is centrifuged 5min. After centrifugal, take 6mL acetonitrile extraction liquid and be transferred to equipped with 900mg anhydrous magnesium sulfate, 300mgC18With in the centrifuge tube of 150mgPSA, vortex 1min, 5000r/min are centrifuged 5min.Take 4mL supernatant in nitrogen blowpipe, dry up in 40 DEG C of nitrogen, add acetone/normal hexane mixed solvent dissolved residue that 1mL volume ratio is 1/1, after vortex mixed film, move in sample injection bottle and treat that GC-EI-MS measures.
(2) preparation of standard working solution
Accurately weighing 25 �� 0.1mg standard substance in 25mL volumetric flask, dissolve with acetonitrile, constant volume obtains 1000.0 �� g/mL standard reserving solutions; Pipette 1.0mL standard reserving solution and be placed in 100mL volumetric flask, obtain 10.0 �� g/mL standard intermediate liquids with the acetone that volume ratio is 1/1/normal hexane mixed solvent constant volume; 10 �� g/mL standard solution dilutions are made into 5,2,1,0.5,0.2,0.1 �� g/mL standard solution. The Fructus Mali pumilae blank sample of not fluorine-containing ether bacterium amide is processed by above-mentioned pre-treatment step, obtain sample extraction and purify residue, this residue adds acetone/normal hexane mixed solvent and the 100 above-mentioned mixed standard solutions of �� L that 900 �� L volume ratios are 1/1, vortex mixes, and is made into 10,20,50,100,200,500 �� g/L extraction standard working solutions.
(3) gas chromatogram-electron impact ion source-mass spectrography (GC-EI-MS) measures
The standard working solution of variable concentrations gradient is injected separately into GC-EI-MS, carries out the quantitative analysis of fluorine ether bacterium amide content with external standard method, namely with the chromatographic peak area of standard working solution, its respective concentration is carried out regression analysis, obtain standard curve; Under the same conditions sample extracting solution is injected GC-EI-MS to be measured, record the chromatographic peak area of fluorine ether bacterium amide in sample liquid, substitute into standard curve, obtaining fluorine ether bacterium amide content in sample liquid, then the Mass Calculation of sample representated by liquid obtains fluorine ether bacterium amide 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 ��m.
Injector temperature: 250.0 DEG C, sample introduction pattern: Splitless injecting samples, sample size: 1 �� 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 with the speed of 20 DEG C per minute, then rises to 220 DEG C with the speed of 2 DEG C per minute, then rises to 280 DEG C 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 solvent delay time is 10min.
The ion of SIM monitoring is: 381,382,397,211, and quota ion is 381.
Qualitative Identification: at identical conditions, if sample liquid Pesticides chromatographic peak retention time pesticide retention time corresponding to standard solution is consistent, and in the sample mass spectrum after background correction, selected ion all occurs, and abundance of ions is more consistent than the abundance of ions ratio with standard solution, then can determine whether sample liquid exists this pesticide; If above-mentioned two condition can not meet simultaneously, then judge without this kind of pesticide.
With the chromatographic peak area of standard working solution, its respective concentration is carried out regression analysis, obtain standard working curve such as table 1.
The standard curve of fluorine ether bacterium amide in table 1 Fructus Mali pumilae bare substrate
| Title | Retention time (min) | Regression equation | Correlation coefficient |
| Fluorine ether bacterium amide LH-2010A | 18.14 | Y=4136.4X-59247 | 0.9995 |
Recovery of standard addition and repeatability:
The Fructus Mali pumilae of not fluorine-containing ether bacterium amide adds the fluorine ether bacterium amide standard solution of 10,20 and 200 g/kg3 concentration levels of ��, adds until pesticide and carry out the determination of residual amount by above-mentioned process step after 30min.Mensuration concentration and pesticide theory being added concentration compare, obtain pesticide TIANZHU XINGNAO Capsul, each pitch-based sphere parallel assay 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 amide is 95.5%��99.0%, and average relative standard's deviation (RSD) is 4.5%��4.9%, illustrates that the response rate of the inventive method is higher, reproducible.
The response rate of table 2 fluorine ether bacterium amide and repeatability (n=6)
Detection limit:
The fluorine ether bacterium amide substrate standard working solution of variable concentrations is injected GC-EI-MS, calculating detection limit with the cycles of concentration (cycles of concentration of Fructus Mali pumilae is for 2.0 times) of 3 times of signal to noise ratios of least concentration extraction standard solution chromatographic peak and sample handling processes, the detection of fluorine ether bacterium amide is limited to 0.97 �� g/kg.
Embodiment 2: the detection of fluorine ether bacterium amide residual quantity in dehydration Capsicum annuum L.
(1) sample pre-treatments
Weigh the dehydration Capsicum annuum L. 2.0g through fully mixing in 50mL centrifuge tube, after adding 5mL water recovery 30min, accurately add the 20mL acetonitrile solution containing 1% acetic acid, homogenizing extracts 1min, adding 3g anhydrous magnesium sulfate, 2g sodium acetate and 2mL water, after vortex 1min, 7000r/min is centrifuged 5min. After centrifugal, take 6mL acetonitrile extraction liquid and be transferred to equipped with 900mg anhydrous magnesium sulfate, 300mgC18With in the centrifuge tube of 150mgPSA, vortex 1min, 5000r/min are centrifuged 5min. Take 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
Acetone/normal hexane mixed solvent that 1000ng/mL standard reserving solution volume ratio is 1/1 is diluted to 10ng/mL standard intermediate liquid, 10 �� g/mL standard solution dilutions are made into 5,2,1,0.5,0.2,0.1 �� g/mL standard solution. The dehydration Capsicum annuum L. blank sample of not fluorine-containing ether bacterium amide is processed by above-mentioned pre-treatment step, obtain sample extraction and purify residue, this residue adds acetone/normal hexane mixed solvent and the 100 above-mentioned mixed standard solutions of �� L that 900 �� L volume ratios are 1/1, vortex mixes, and is made into 10,20,50,100,200,500 �� g/L extraction standard working solutions.
(3) gas chromatogram-electron impact ion source-mass spectrography (GC-EI-MS) measures
Operating procedure, chromatograph are consistent with the mensuration of fluorine ether bacterium amide in above-mentioned Fructus Mali pumilae sample with Mass Spectrometry Conditions.
Qualitative Identification:
Consistent with the mensuration of fluorine ether bacterium amide in above-mentioned Fructus Mali pumilae sample.
Linear relationship:
With the chromatographic peak area of standard working solution, its respective concentration being carried out regression analysis, obtaining standard working curve is Y=7660.2X-109545, and correlation coefficient is 0.9994.
Recovery of standard addition and repeatability:
The dehydration Capsicum annuum L. of not fluorine-containing ether bacterium amide adds the fluorine ether bacterium amide standard solution of 50,100 and 200 g/kg3 concentration levels of ��, add until pesticide and carry out the determination of residual amount by above-mentioned process step after 30min, mensuration concentration and pesticide theory are added concentration compare, obtain pesticide TIANZHU XINGNAO Capsul, each pitch-based sphere parallel assay 6 times, obtaining 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 amide is 93.5%��96.3%, and average relative standard's deviation (RSD) is 3.7%��5.5%, illustrates that the response rate of the inventive method is high, reproducible.
The response rate of table 3 fluorine ether bacterium amide and repeatability (n=6)
Detection limit:
The fluorine ether bacterium amide substrate standard working solution of variable concentrations is injected GC-EI-MS, calculating detection limit with the cycles of concentration (cycles of concentration of dehydration Capsicum annuum L. is for 0.4 times) of 3 times of signal to noise ratios of least concentration extraction standard solution chromatographic peak and sample handling processes, the detection of fluorine ether bacterium amide is limited to 2.53 �� g/kg.
Above embodiments is only that the preferred embodiment of the present invention is described; not the scope of the present invention is defined; under the premise designing spirit without departing from the present invention; various modification that technical scheme is made by this area ordinary skill technology and improvement, all should fall in the protection domain that claims of the present invention are determined.
Claims (4)
1. a GC-EI-MS measures the method for fluorine ether bacterium amide residual in fruit and vegerable, it is characterised in that said method comprising the steps of:
(1) extract
Weigh vegetable and fruit sample in tool plug centrifuge tube, add acetonitrile or the acetonitrile solution homogenizing containing 1% acetic acid extracts 1min, add the one in sodium chloride or sodium acetate and centrifugal after anhydrous magnesium sulfate vibration;
(2) purify
Pipette sample extracting solution supernatant in centrifuge tube, add Dispersive solid phase extraction agent, vortex oscillation, centrifugal, take after a certain amount of scavenging solution nitrogen dries up, dissolve constant volume with the acetone that volume ratio is 1/1/normal hexane mixed solvent, after crossing film, treat gas chromatogram-electron impact ion source-mass spectrum (GC-EI-MS) detection;
(3) preparation of standard working solution
The same kind matrix blank sample of not fluorine-containing ether bacterium amide is processed by above-mentioned steps (1), (2), obtain sample extraction and purify residue, adding appropriate solvent and standard solution, vortex mixes, and is configured to the fluorine ether bacterium amide series standard working solution of at least 3 concentration;
(4) measure and result calculates
GC-EI-MS analysis condition is: chromatographic column: HP-5MS capillary chromatographic column, column length 30m, internal diameter 0.25mm, thickness 0.25 ��m; Injector temperature 250.0 DEG C; Carrier gas: He, not shunt mode sample introduction, sample size: 1 �� L; Constant current mode, flow velocity 1.0mL/min; Heating schedule: initial temperature 60 DEG C keeps 2min, rises to 200 DEG C with the speed of 20 DEG C per minute, then rises to 220 DEG C with the speed of 2 DEG C per minute, then rises to 280 DEG C 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: 381,382,397,211;
The standard working solution of each Concentraton gradient in step (3) is carried out GC-EI-MS mensuration, with the chromatographic peak area of standard working solution, its respective concentration is carried out regression analysis, obtain extraction standard working curve; Under the same conditions the sample liquid after purification in step (2) is injected GC-EI-MS to be measured, record the chromatographic peak area of fluorine ether bacterium amide in sample liquid, substitute into extraction standard curve, obtaining fluorine ether bacterium amide content in sample liquid, then the Mass Calculation of sample representated by liquid obtains fluorine ether bacterium amide residual quantity in sample per sample.
2. a kind of GC-EI-MS according to claim 1 measures the method for fluorine ether bacterium amide residual in fruit and vegerable, it is characterised in that step (1) if in vegetable and fruit sample dehydrated sample, need to reduce sample weighting amount, and add suitable quantity of water and fully infiltrate.
3. a kind of GC-EI-MS according to claim 1 measures the method for fluorine ether bacterium amide residual in fruit and vegerable, it is characterized in that, step (1) need to add sodium chloride during employing acetonitrile extraction saltout, adopt the acetonitrile solution containing 1% acetic acid need to add sodium acetate when extracting and saltout.
4. a kind of GC-EI-MS according to claim 1 measures the method for fluorine ether bacterium amide residual in fruit and vegerable, it is characterised in that the dispersive solid-phase extraction agent of step (2) mesostroma is by anhydrous magnesium sulfate, C18Form with PSA, anhydrous magnesium sulfate, C in every milliliter of extracting solution18With PSA addition respectively 150mg, 50mg and 25mg.
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| CN105717223A (en) * | 2016-01-30 | 2016-06-29 | 崔淑华 | GC-EI-MS method for determining penflufen residues in fruits and vegetables |
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| CN105572288A (en) * | 2016-01-30 | 2016-05-11 | 郭庆龙 | Method for determining aminobenzene pyrazolone residues in fruits and vegetables through GC-EI-MS |
| CN105675786A (en) * | 2016-01-30 | 2016-06-15 | 崔淑华 | Method for determining fluxapyroxad residues in fruits and vegetables with GC-EI-MS (gas chromatography-electron ionization-mass spectrometry) |
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