CN105717224A - GC-EI-MS method for rapidly determining residual aminobenzene pyrazolone amount - Google Patents

GC-EI-MS method for rapidly determining residual aminobenzene pyrazolone amount Download PDF

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CN105717224A
CN105717224A CN201610070387.7A CN201610070387A CN105717224A CN 105717224 A CN105717224 A CN 105717224A CN 201610070387 A CN201610070387 A CN 201610070387A CN 105717224 A CN105717224 A CN 105717224A
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郭庆龙
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    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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Abstract

The invention discloses a GC-EI-MS method for rapidly determining the residual aminobenzene pyrazolone amount.The method is mainly used for determining the residual aminobenzene pyrazolone amount in animal derived foods with high fat content.Acetonitrile is adopted to homogeneously extract the residual aminobenzene pyrazolone in a sample, the extracting solution is subjected to matrix dispersion and purification of an enhanced matrix removal (EMR) product and extraction by a reverse extraction tube and concentration are conducted, then gas chromatography-electron impact ionization-mass spectrometry (GC-EI-MS) detection is performed, a blank matrix solution containing no pesticide to be detected is adopted to establish a standard working curve for correction, and quantification is performed by adopting an external standard method.The average recovery rate of the method is 92.0%-93.4%, the average relative standard deviation (RSD) of the method is 4.6%-7.0%, the detection limit of the method reaches 2.19 micrograms/kilogram or below, and the method has the advantages of being simple and convenient to operate, rapid, good in impurity removal effect, high in sensitivity, good in characteristic performance and repeatability and accurate in qualititation and quantification, can meet the technical requirements for corresponding product safety detection of the United States, European Union, Japan and other countries and provides a powerful technical support for ensuring the people's food safety and healthy development of the abroad export trade of our country.

Description

A kind of GC-EI-MS rapid assay methods of amine Phenopyrazone residual quantity
Technical field
The present invention relates to the GC-EI-MS rapid assay methods of a kind of amine Phenopyrazone residual quantity, more specifically use Gas chromatogram-electron impact ion source-mass spectrum (GC-EI-MS) qualitative, quantitative measures the animal fleshes such as Carnis Sus domestica, beef, Carnis caprae seu ovis, Carnis Gallus domesticus In the animal derived food that the fat content such as meat and goods is high, the method for the amine Phenopyrazone content of residual, belongs to persticide residue Determination techniques field.
Background technology
Amine Phenopyrazone (Fenpyrazamine) is the based on pyridine miscellaneous of SUMITOMO CHEMICAL KCC research and development Ring class antifungal, by the pathogen of the mechanism of action of suppression ergosterol biosynthesis pathway, demonstrates mycelial growth With spore germination and the inhibitory action of pollen tube growth.No. CAS is: 473798-59-3, and molecular formula is C17H21N3O2S, molecular weight Being 331.43, the chemical structural formula of amine Phenopyrazone is as follows:
Amine benzene pyrrole bacterium ketone is the novel germicide of Sumitomo Chemical stand-alone development, has novel chemical constitution, can rapidly permeate into work In object, to the fungus energy fast onset drug effect infected, it is mainly used in gray mold, the bacterium controlling in Fructus Vitis viniferae, carpolities, vegetable crop Core disease and chain sclerotinia sclerotiorum.It addition, amine benzene pyrrole bacterium ketone is to mammal high safety, can degrade rapidly in the environment, can be many Plant before crop is gathered and apply.Amine benzene pyrrole bacterium ketone is initially released in Korea S, obtains first whole world registration at the amine benzene pyrrole former medicine of bacterium ketone After, Sumitomo Chemical releases its antibacterial new product containing the amine benzene pyrrole former medicine of bacterium ketone in Korea S again, and carries out with Botrycide trade (brand) name Selling, this product is the suspending agent type of 30%, for fruits and vegetables crop.2009, Sumitomo Chemical was in the registration of application European Union The vegetable crops such as Fructus Lycopersici esculenti, Fructus Solani melongenae, Fructus Capsici and the calabash for greenhouse production, the also Field information of Fructus Vitis viniferae, but the most only exist Poland obtains the interim registration of 3 years by a definite date, trade name Prolectu.In June, 2012, European Union's food is managing with animal health Committee has voted its registration application through, and amine benzene pyrrole bacterium ketone has obtained European Union's approval registration, will be on January 1st, 2013 Rising and formally list the registered effective ingredient list under European Union's pesticide 1107/2009 regulation in, effect duration is 10 years.Amine benzene pyrrole bacterium ketone After European Union obtains registration, Fructus Vitis viniferae and some chamber crops will be used for, such as Fructus Lycopersici esculenti, Fructus Solani melongenae, Fructus Capsici and calabash etc..Amine benzene pyrrole bacterium ketone Have excellent prevention and control ability to botrytis, Sumitomo Chemical will push away to Italy and Chile market in 2012/13 year further This product wide, its whole world trade name Prolectus.Registered in the U.S. and a lot of Asian countries, had the widest Wealthy application prospect.
Along with amine Phenopyrazone registration, promote and use, as China's main exit market European Union, the U.S., add and take Big grade national has formulated its maximum allowable residual quantity (MRL) in the food agricultural product such as veterinary antibiotics, Cereals and livestock products, European Union formulates antibacterial amine benzene pyrrole bacterium ketone MRL standard in various crop.This standard is on May 7th, 2012 Come into force.Amine benzene pyrrole bacterium ketone MRL in Rhizoma Solani tuber osi, Fructus Capsici, Fructus Solani melongenae is 3mg/kg；Calabash, Fructus Cucumidis sativi, Gherkin, MRL in Courgettes is 0.7mg/kg；Residual in the fruit such as Citrus, grapefruit, Fructus Citri Limoniae and various dry fruit Limit the quantity most stringent, for 0.01mg/kg.The U.S. specifies that amine Phenopyrazone MRL in Semen Armeniacae Amarum is 0.02mg/kg； MRL in Semen Armeniacae Amarum shell is 1.5mg/kg；MRL in Fructus Pistaciae Verae is 0.02mg/kg；At lettuce MRL in lettuce head is 1.5mg/kg；MRL in leaf lettuce is 2mg/kg；In cranberry subgroup MRL in 13-07A is 5mg/kg；MRL in bush fruit class subgroup 13-07B is 5mg/ kg；In small-sized fruit 13-07F subgroup of overgrowing, the MRL of (in addition to Fructus actinidiae chinensis) is 3mg/kg；In Sucus Vitis viniferae MRL is 4mg/kg；MRL in short youngberry class subgroup 13-07G is 3mg/kg；In Radix Ginseng MRL be 0.7mg/kg.Canada's regulation amine Phenopyrazone is at Sucus Vitis viniferae, Caulis et Folium Lactucae Sativae, Caulis et Folium Lactucae sativae, Radix Ginseng, Semen Armeniacae Amarum heavily fortified point Really, the M RL in Fructus Pistaciae Verae is respectively 4.0mg/kg, 2.0mg/kg, 1.5mg/kg, 0.7mg/kg and 0.02mg/kg；European Union, day When national regulation such as this grade does not formulate the residue limits standard of corresponding pesticide, the food agricultural product being exported to its country include poultry In the animal derived foods such as meat, residue limits all carries out " uniform limit " of 0.01mg/L.
Present stage, the research to amine Phenopyrazone determination of residual amount method is less, and the detection method of report is mainly vegetable With amine Phenopyrazone method for detecting residue in fruit, these detection methods all use Liquid Chromatography-Tandem Mass Spectrometry (LC-MS/MS) to survey Determine the detection method of amine Phenopyrazone residual quantity in vegetable and fruit, use LC-MS/MS to measure food Residual Pesticides in Farm Produce There is quick, easy, sensitivity advantages of higher, but due to its price costly, a lot of testing agencies, enterprise or scientific research institutions are not Configure this instrument or configuration number of units is less, when using LC-MS/MS detection due to different compounds, different flowings need to be used Mutually or chromatographic column, such needs are constantly changed chromatographic column, flowing and mutually and are expended the long time and be balanced system, this Determine to constrain in degree the application of LC-MS/MS.The gaschromatographic mass spectrometry (GC-EI-MS) being equipped with electron impact ionization source analyzes food Product Residual Pesticides in Farm Produce tool has great advantage, and owing to electron impact ionization source mass spectrum is versatility detector, can realize several The multi-residue analysis of hundred kinds of pesticide, can be the most qualitative and quantitative, moderate, and therefore existing various testing agencies and enterprise are equipped with Pesticide residues in food agricultural product are detected by gas chromatogram-electron impact ion source-mass spectrograph (GC-EI-MS), but so far The report of the GC-EI-MS detection method of amine Phenopyrazone residual quantity in food agricultural product is had no till the present.Additionally, it is well known that, QuEChERS pretreatment technology has become sample-pretreating method most widely used in pesticide residue analysis, but QuEChERS method It is primarily adapted for use in the High water cut substrate of low-fat content, such as most fruit and vegetable, energy when in the face of high fat content substrate Power is limited, it is generally required to increase normal hexane grease removal, freezing sample extracting solution goes the steps such as fat, but effect is limited.In recent years some Company is proposed enhancement mode lipid and removes patented product-Enhanced Matrix Removal, EMR-lipid, is mainly used in Remove the lipid chaff interference with straight chain hydrocarbon structure, including free fatty, cholesterol, triglyceride, phospholipid etc..This product is Be made into matrix solid phase dispersion extractant, hydroactivated after can directly by dispersive solid-phase extraction flow process to the lipid in extracting solution Impurity is removed, and the present invention applies this pre-treating method to find when purifying animal derived food, and the method is simply efficient, to fat Class material removal effect is good, sets up EMR substrate and disperses purification, gas chromatogram-electron impact ion source-mass spectrum (GC-EI-MS) fixed In property and quantitative analysis animal derived food, the detection method of amine Phenopyrazone residual quantity is significant.
Summary of the invention
It is an object of the invention to provide the GC-EI-MS rapid assay methods of a kind of amine Phenopyrazone residual quantity, be mainly used in Measure amine Phenopyrazone residual quantity in the food agricultural product that the fat contents such as animal derived food are high.
For realizing object above, the technical solution adopted in the present invention is: the GC-EI-of a kind of amine Phenopyrazone residual quantity MS rapid assay methods, comprises the steps:
(1) extract
Weigh mixing sample in tool plug centrifuge tube in, add suitable quantity of water recovery after, be quantitatively adding acetonitrile solution homogenizing extract, then Add sodium chloride and anhydrous magnesium sulfate, centrifugal after violent vortex 1min.
Purify
By enhancement mode lipid remove product E MR use water activation, pipette sample extracting solution in activate EMR purification pipe in, vortex After 1min, 7000r/min is centrifuged 5min, shifts whole supernatant to carrying out equipped with in the centrifuge tube of anhydrous magnesium sulfate and sodium chloride Saltout, after vortex centrifugal, pipette the supernatant of certain volume, after being concentrated to dryness, mix with acetone/normal hexane that volume ratio is 1/1 Bonding solvent dissolves constant volume, after crossing film, treats gas chromatogram-electron impact ion source-mass spectrum (GC-EI-MS) detection.
(3) preparation of standard working solution
Same kind matrix blank sample without amine Phenopyrazone is processed by above-mentioned steps (1), (2), obtains sample extraction and purify Residue, adds appropriate solvent and standard solution, and vortex mixes, and is configured to the amine Phenopyrazone series standard work of at least 3 concentration Make liquid.
(4) measure and result calculates
The standard working solution of each Concentraton gradient in step (3) is carried out GC-EI-MS mensuration, with the chromatographic peak of standard working solution Area carries out regression analysis to its respective concentration, obtains extraction standard working curve；Step (2) will be purified under the same conditions After sample liquid inject GC-EI-MS and be measured, record the chromatographic peak area of amine Phenopyrazone in sample liquid, substitute into substrate mark Quasi-working curve, obtains amine Phenopyrazone content in sample liquid, then obtains according to the Mass Calculation of sample representated by sample liquid Amine Phenopyrazone residual quantity in sample；If amine Phenopyrazone residual quantity exceedes the range of linearity upper limit in upper machine solution, constant volume need to be used Within upper machine solution concentration is diluted to the range of linearity by solvent.
Step (1) if in the sample of the moisture content less such as sample animal livers, suitable quantity of water must be added before extraction and fully infiltrate.
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 with the speed of 20 DEG C per minute, then with per minute 2 DEG C speed rise to 220 DEG C, then rise to 280 DEG C with the speed of 20 DEG C per minute, keep 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: electron bombardment Ionization, i.e. EI pattern, energy 70eV；Scan mode: Salbutamol Selected Ion Monitoring (SIM) pattern, the ion of monitoring is: 230.1, 331.1、256.1、231.1。
When step (4) measures sample liquid and extraction standard working solution, if sample liquid Pesticides chromatographic peak retention time and mark In quasi-solution, corresponding pesticide retention time is consistent, and in the sample mass spectrum after background correction, selected ion is equal Occur, and abundance of ions is more consistent than the abundance of ions ratio with standard solution, then can determine whether to exist in sample liquid 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, establishes simplicity, quickly and can be prevented effectively from the interference of sample mesostroma Sample-pretreating method, this pre-treating method is combined GC-EI-MS and is applied to amine benzene pyrazoles in Cereals, animal derived food The qualitative confirmation of ketone and detection by quantitative, average recovery rate is 92.0%～93.4%, and average relative standard's deviation (RSD) is 4.9% ～7.0%, detection limit is less than 2.19 μ g/kg, has easy and simple to handle, quick, accurate, highly sensitive and reproducible advantage. The U.S., European Union, the Japan and other countries technology requirement to corresponding product safety detection can be met, for ensureing our people's food safety And export abroad trade sound development provides strong technical support.
Accompanying drawing explanation
Fig. 1 is that the GC-EI-MS being added on the amine Phenopyrazone in blank Carnis Sus domestica substrate selects chromatography of ions figure.
Fig. 2 is that the GC-EI-MS of the Carnis Sus domestica blank sample without amine Phenopyrazone selects chromatography of ions figure.
Fig. 3 is the amine Phenopyrazone standard work song with the Carnis Sus domestica blank sample without amine Phenopyrazone as substrate preparation Line.
Detailed description of the invention
Now with following embodiment, the present invention is described, but is not to limit the scope of the present invention.
The instrument used in embodiment and reagent
T18Basic homogenizer (IKA, Germany)；CR21G III centrifuge (Hitachi, Japan)；MS3 basic model vortex mixer (IKA, Germany)；TurboVap LV pattern product automatic concentration instrument (Caliper, USA)；7890N gas chromatogram-5977C matter Spectrometer (Agilent, USA)；Enhancement mode lipid is removed product (Enhanced Matrix Removal, EMR) and is purchased from U.S.'s peace victory Lun Science & technology Co., Ltd.
Reagent
Acetonitrile, acetone, normal hexane (HPLC level, Merke, Germany)；Anhydrous magnesium sulfate, sodium chloride are analytical pure, are purchased from state Chemical reagent company limited of medicine group.
Standard substance: purity 98.0%, purchased from Japan and Guang Chun agro-industry Co., Ltd..
Embodiment 1: the detection of amine Phenopyrazone residual quantity in Carnis Sus domestica
(1) sample pre-treatments
Extract
Weigh through the abundant 5g Carnis Sus domestica sample mixed in 50mL centrifuge tube, after adding 10mL water recovery 30min, accurately add 20mL acetonitrile solution, mechanical shaking extraction 20min, supersound extraction 5min, add 3g anhydrous magnesium sulfate and 2g sodium chloride, vortex 1min After, after 7000r/min is centrifuged 5min, to be clean.
Purify
Addition 4mL water is in the purification pipe removing product E MR equipped with enhancement mode lipid, and vortex makes it fully activate, and pipettes 6mL sample Product extracting solution is in the EMR activated purifies pipe, and after vortex 1min, 7000r/min is centrifuged 5min, shifts whole supernatant to dress Have in the centrifuge tube of anhydrous magnesium sulfate and sodium chloride and saltout, after vortex centrifugal, pipette 4mL supernatant, after being concentrated to dryness, use Volume ratio is acetone/normal hexane mixed solvent dissolving constant volume of 1/1, after crossing film, treats gas chromatogram-electron impact ion source-matter Spectrum (GC-EI-MS) detection.
(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 μ g/mL standards storages Standby liquid；Pipette 1.0mL standard reserving solution to be placed in 100mL volumetric flask, with molten with the acetone that volume ratio is 1/1/normal hexane mixing Agent constant volume obtains 10.0 μ g/mL standard intermediate liquids；10 μ g/mL standard solution dilutions are made into 5,2,1,0.5,0.2,0.1 μ g/mL Standard solution.Carnis Sus domestica blank sample without amine Phenopyrazone is processed by above-mentioned pre-treatment step, obtains sample extraction and purify residual Slag, adds acetone/normal hexane mixed solvent and the 100 above-mentioned standard solution of μ L, whirlpool that 900 μ L volume ratios are 1/1 in this residue Rotation mixing, is made into 10,20,50,100,200,500 μ 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 determining of amine Phenopyrazone content with external standard method Component analysis, i.e. carries out regression analysis with the chromatographic peak area of standard working solution to its respective concentration, obtains standard working curve；? Under the same terms, sample extracting solution is injected GC-EI-MS to be measured, record the chromatographic peak face of amine Phenopyrazone in sample liquid Long-pending, substitute into standard working curve, obtain amine Phenopyrazone content in sample liquid, then according to the quality of sample representated by sample liquid It is calculated amine Phenopyrazone residual quantity in 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.
Furnace box heating schedule: initial temperature 60 DEG C keeps 2min, rises to 200 DEG C with the speed of 20 DEG C per minute, then with every point The speed that clock is 2 DEG C rises to 220 DEG C, 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: 150 DEG C；Quadrupole rod temperature 150 DEG C.
Scan mode: Salbutamol Selected Ion Monitoring (SIM) pattern；The ion of SIM monitoring is: 230.1,331.1,256.1, 231.1；Quota ion is 230.1.
Qualitative Identification: at identical conditions, if sample liquid Pesticides chromatographic peak retention time is corresponding to standard solution Pesticide retention time is consistent, and in the sample mass spectrum after background correction, selected ion all occurs, and ion Abundance ratio is consistent with the abundance of ions ratio of standard solution, then can determine whether to exist in sample liquid this pesticide；If above-mentioned two condition Can not meet simultaneously, then judge without this kind of pesticide.
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= 1291.77X-13186.36, correlation coefficient is 0.9992.
Recovery of standard addition and repeatability:
The amine Phenopyrazone standard adding 10,20 and 200 3 concentration levels of μ g/kg in the Carnis Sus domestica without amine Phenopyrazone is molten Liquid, carries out the determination of residual amount by above-mentioned process step after pesticide adds 30min, and with pesticide theory, mensuration concentration is added concentration Compare, obtain pesticide TIANZHU XINGNAO Capsul, each pitch-based sphere parallel assay 6 times, obtain its relative standard deviation, measurement result It is shown in Table 1.As can be seen from Table 1, in 3 mark-on levels, the average recovery rate of amine Phenopyrazone is 92.0%～93.4%, flat All relative standard deviations (RSD) are 4.9%～7.0%, illustrate that the response rate of the inventive method is high, reproducible.
The response rate of table 1 amine Phenopyrazone and repeatability (n=6)
Detection limit:
The amine Phenopyrazone extraction standard working solution of variable concentrations is injected GC-EI-MS, with least concentration extraction standard solution 3 times of signal to noise ratios of chromatographic peak and the cycles of concentration (cycles of concentration of Carnis Sus domestica is 1.0 times) of sample handling processes calculate detection limit, amine The detection of Phenopyrazone is limited to 2.19 μ g/kg.
Above embodiment is only to be described the preferred embodiment of the present invention, not carries out the scope of the present invention Limiting, on the premise of designing spirit without departing from the present invention, technical scheme is made by this area ordinary skill technology Various modification and improvement, all should fall in the protection domain that claims of the present invention determines.

Claims (3)

1. the GC-EI-MS rapid assay methods of an amine Phenopyrazone residual quantity, it is characterised in that described method includes following Step:
(1) extract
Weigh mixing sample in tool plug centrifuge tube in, after adding suitable quantity of water, add acetonitrile solution homogenizing extract after, add sodium chloride and Anhydrous magnesium sulfate, centrifugal after violent vortex 1min；
(2) purify
By enhancement mode lipid remove product E MR use water activation, pipette sample extracting solution in activate EMR purification pipe in, vortex After 1min, 7000r/min is centrifuged 5min, shifts whole supernatant to carrying out equipped with in the centrifuge tube of anhydrous magnesium sulfate and sodium chloride Saltout, after vortex centrifugal, pipette the supernatant of certain volume, after being concentrated to dryness, mix with acetone/normal hexane that volume ratio is 1/1 Bonding solvent dissolves constant volume, after crossing film, treats gas chromatogram-electron impact ion source-mass spectrum (GC-EI-MS) detection；
(3) preparation of standard working solution
Same kind matrix blank sample without amine Phenopyrazone is processed by above-mentioned steps (1), (2), obtains sample extraction and purify Residue, adds appropriate solvent and standard solution, and vortex mixes, and is configured to the amine Phenopyrazone series standard work of at least 3 concentration Make liquid；
(4) measure and result calculates
The standard working solution of each Concentraton gradient in step (3) is carried out GC-EI-MS mensuration, with the chromatographic peak of standard working solution Area carries out regression analysis to its respective concentration, obtains extraction standard working curve；Step (2) will be purified under the same conditions After sample liquid inject GC-EI-MS and be measured, record the chromatographic peak area of amine Phenopyrazone in sample liquid, substitute into substrate mark Quasi-working curve, obtains amine Phenopyrazone content in sample liquid, then obtains according to the Mass Calculation of sample representated by sample liquid Amine Phenopyrazone residual quantity in sample；If amine Phenopyrazone residual quantity exceedes the range of linearity upper limit in upper machine solution, constant volume need to be used Within upper machine solution concentration is diluted to the range of linearity by solvent.
The GC-EI-MS rapid assay methods of a kind of amine Phenopyrazone residual quantity the most according to claim 1, its feature exists In, step (1) if in the sample of sample moisture content less, suitable quantity of water must be added before extraction and fully infiltrate.
The GC-EI-MS rapid assay methods of a kind of amine Phenopyrazone residual quantity the most according to claim 1, its feature exists In, in step (4), 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 with the speed of 20 DEG C per minute, then with per minute 2 DEG C speed rise to 220 DEG C, then rise to 280 DEG C with the speed of 20 DEG C per minute, keep 10min；Transmission line temperature: 280 DEG C；Electricity From pattern: electron impact ionization, i.e. EI pattern, energy 70eV；Ion source temperature 150 DEG C；Scan mode: Salbutamol Selected Ion Monitoring (SIM) pattern, the ion of monitoring is: 230.1,331.1,256.1,231.1.
CN201610070387.7A 2016-01-30 2016-01-30 GC-EI-MS method for rapidly determining residual aminobenzene pyrazolone amount Pending CN105717224A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108414639A (en) * 2018-03-27 2018-08-17 山东五洲检测有限公司 A kind of rapid detection method of Pesticide Residues object
CN110907547A (en) * 2019-11-20 2020-03-24 上海交通大学 Method for rapidly detecting polycyclic aromatic hydrocarbon in milk with low solvent consumption

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014101319A (en) * 2012-11-21 2014-06-05 Nissan Chem Ind Ltd Germicide, nematicide or bactericide compositions
CN103843794A (en) * 2012-12-07 2014-06-11 陕西美邦农药有限公司 Efficient fungicidal composition containing fenpyrazamine
CN104535686A (en) * 2014-12-30 2015-04-22 山东出入境检验检疫局检验检疫技术中心 GC-NCI-MS determination method for cyenopyrafen residual quantity

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014101319A (en) * 2012-11-21 2014-06-05 Nissan Chem Ind Ltd Germicide, nematicide or bactericide compositions
CN103843794A (en) * 2012-12-07 2014-06-11 陕西美邦农药有限公司 Efficient fungicidal composition containing fenpyrazamine
CN104535686A (en) * 2014-12-30 2015-04-22 山东出入境检验检疫局检验检疫技术中心 GC-NCI-MS determination method for cyenopyrafen residual quantity

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
LIMIAN ZHAO 等: "《http://cn.agilent.com/cs/library/applications/5991-6097CHCN.pdf》", 4 August 2015, 安捷伦科技（中国）有限公司 *
PARK,HYEJI 等: "Development and validation of an analytical method for fungicide fenpyrazamine determination in agricultural products by HPLC-UVD", 《ANALYTICAL SCIENCE & TECHNOLOGY》 *
SUSAN STRANGE HERRMANN 等: "《www.eurl-pesticides.eu/docs/public/tmplt_article.asp?LabID=400&CntID=618&Theme_ID=1&Pdf=False&Lang=EN》", 31 December 2015 *
杨淑娴 等: "胺苯吡菌酮原药的液相色谱分析方法研究", 《农药科学与管理》 *
柳彩云 等: "气相色谱-质谱法测定纺织品中22种农药残留", 《理化检验（化学分册）》 *
郭永泽 等: "农产品中多种农药残留的气相色谱-质谱联用方法", 《分析测试学报》 *
高玉生 等: "气相色谱-质谱法同时测定土壤中30种农药残留", 《理化检验（化学分册）》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108414639A (en) * 2018-03-27 2018-08-17 山东五洲检测有限公司 A kind of rapid detection method of Pesticide Residues object
CN110907547A (en) * 2019-11-20 2020-03-24 上海交通大学 Method for rapidly detecting polycyclic aromatic hydrocarbon in milk with low solvent consumption
CN110907547B (en) * 2019-11-20 2021-07-16 上海交通大学 Method for rapidly detecting polycyclic aromatic hydrocarbon in milk with low solvent consumption

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