CN105699521A - GC-MS/MS (Gas Chromatography-Mass Spectrometer/Mass Spectrometer) rapid determination method for residual amount of ametoctradin - Google Patents

Abstract

The invention discloses a GC-MS/MS (Gas Chromatography-Mass Spectrometer/Mass Spectrometer) rapid determination method for the residual amount of ametoctradin. The method is mainly used for determining the content of residual ametoctradin in animal-derived foods with high fat content. The method comprises the following steps: homogenizing and extracting residual ametoctradin in a sample; dispersing and purifying an extracting solution through enhanced matrix removal (EMR), and extracting and concentrating by a reverse extraction pipe; detecting by gas chromatography-mass spectrometer/mass spectrometer (GC-MS/MS); and establishing a corrected standard working curve by adopting a blank matrix solution without pesticides to be detected, and quantifying by an external standard method. According to the method, the average recovery rate is 91.3%-99.0%, the average relative standard deviation is 5.2%-8.6% and the detection limit is lower than 6.74mu g/kg. The GC-MS/MS rapid determination method has the advantages of simplicity and rapidness in operation, good impurity removing effect, high sensitivity, strong characteristics and good repeatability and is accurately qualitative and quantitative.

Description

A kind of GC-MS/MS rapid assay methods of benzene azoles mepanipyrim residual quantity

The invention discloses the GC-MS/MS rapid assay methods of a kind of benzene azoles mepanipyrim residual quantity, the method is mainly used in measuring the method for the benzene azoles mepanipyrim content of residual in the animal derived food that fat content is high。The benzene azoles mepanipyrim of residual in sample is extracted with acetonitrile homogenizing, the enhanced type lipid of extracting solution removes product (EnhancedMatrixRemoval, EMR) substrate dispersion purifies, back extraction pipe extracts after concentrating, gas chromatogram tandem mass spectrum (GC-MS/MS) detects, the vehicle solution without pesticide to be measured is adopted to set up the standard working curve of correction, quantified by external standard method。This method average recovery rate is 91.3%～99.0%, average relative standard's deviation (RSD) is 5.2%～8.6%, detection limit lower than 6.74 μ g/kg, have easy and simple to handle, quick, roguing is effective, highly sensitive, characteristic is strong, reproducible, qualitative, quantitative advantage accurately。The U.S., European Union, the Japan and other countries technology requirement to corresponding product safety detection can be met, for ensureing that our people's food safety and export abroad trade sound development provide strong technical support。

1. the GC-MS/MS rapid assay methods of a benzene azoles mepanipyrim residual quantity, it is characterised in that said method comprising the steps of:

(1) extract

Weigh mixing sample in tool plug centrifuge tube, after adding suitable quantity of water, after adding the extraction of acetonitrile solution homogenizing, add sodium chloride and anhydrous magnesium sulfate, centrifugal after violent vortex 1min；

(2) purify

Enhancement mode lipid is removed product E MR water activate, pipette sample extracting solution and purify in pipe in the EMR activated, after vortex 1min, 7000r/min is centrifuged 5min, shifts whole supernatant and saltouts to the centrifuge tube equipped with anhydrous magnesium sulfate and sodium chloride, after vortex centrifugal, pipette the supernatant of certain volume, be concentrated into after doing, dissolve constant volume with the acetone that volume ratio is 1/1/normal hexane mixed solvent, after crossing film, treat that gas chromatogram tandem mass spectrum (GC-MS/MS) detects；

(3) preparation of standard working solution

Same kind matrix blank sample without benzene azoles mepanipyrim 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 benzene azoles mepanipyrim series standard working solution of at least 3 concentration；

(4) measure and result calculates

The standard working solution of each Concentraton gradient in step (3) is carried out GC-MS/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-MS/MS to be measured, record the chromatographic peak area of benzene azoles mepanipyrim in sample liquid, substitute into extraction standard working curve, obtaining benzene azoles mepanipyrim content in sample liquid, then the Mass Calculation of sample representated by liquid obtains benzene azoles mepanipyrim residual quantity in sample per sample；If benzene azoles mepanipyrim residual quantity exceedes the range of linearity upper limit in upper machine solution, with constant volume solvent, upper machine solution concentration need to be diluted within the range of linearity。

2. the GC-MS/MS rapid assay methods of a kind of benzene azoles mepanipyrim residual quantity according to claim 1, it is characterised in that step (1) if in the sample of sample moisture content less, suitable quantity of water must be added before extraction and fully infiltrate。

3. the GC-MS/MS rapid assay methods of a kind of benzene azoles mepanipyrim residual quantity according to claim 1, it is characterized in that, in step (4), GC-MS/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 1.2mL/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: 290 DEG C；Ionization pattern: electron impact ionization (EI, 70eV)；Ion source temperature 280 DEG C；Collision gas: argon；Multiple-reaction monitoring scan mode MRM, monitoring parameter is:

A kind of GC-MS/MS rapid assay methods of benzene azoles mepanipyrim residual quantity

Technical field

The present invention relates to the GC-MS/MS rapid assay methods of a kind of benzene azoles mepanipyrim residual quantity, more specifically adopt gas chromatogram tandem mass spectrum (GC-MS/MS) qualitative, quantitative to measure the method for the benzene azoles mepanipyrim content of residual in the animal derived food that the fat contents such as animal muscle and goods such as Carnis Sus domestica, beef, Carnis caprae seu ovis, Carnis Gallus domesticus are high, belong to the determination techniques field of persticide residue。

Background technology

Benzene azoles mepanipyrim (Ametoctradin) is the new type bactericide of BASF AG's exploitation, and commodity are called Initium, and chemical name is: 5-ethyl-6-octyl group [1,2,4] triazol [1,5-a] pyrimidine-7-amine, chemical formula is C15H25N5, and structural formula is:

Benzene azoles mepanipyrim (Ametoctradin) belongs to s-triazolo pyrimidines, and it plays a role as a kind of mitochondrial respiratory function inhibitor, can prevent and treat Oomycete fungal disease, for instance downy mildew and various epidemic disease。Ametoctradin first or ratified in European Union and South America in 2010, now obtain registration in multiple country such as the U.S. and Italy, registration product includes single-activity besieged city code name and is BAS65000F (ametoctradin200 g/l) product and two kinds of brand names are that (both of which is containing ametoctradin300 g/l+dimethomorph226 g/l for Zampro and Orvego, dimethomorph) complex preparation product, the complex preparation that it and dimethomorph are made is mainly used in controlling to be easily generated the disease of resistance。BAS65000F is registered for fruit tree, vegetable and Fols lupuli, and Zampro is for fruit tree, vegetable, Fructus Vitis viniferae and Rhizoma Solani tuber osi, and Orvego is then for ornamental crops。Estimate that their annual sales amount is up to 1,200,000,000 Euros, has a extensive future。

Along with the registration of benzene azoles mepanipyrim, popularization and use, it has been formulated residue limits standard by the USA and EU as China's veterinary antibiotics main exit market。European Union specifies that its maximum allowable residue limits in numerous food agricultural product is 0.01～50mg/kg, if Japan and other countries regulation field uses pesticide not register in this country, 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。

Present stage, the research of benzene azoles mepanipyrim determination of residual amount method is less, the detection method of report is mainly in vegetable and fruit benzene azoles mepanipyrim method for detecting residue, these detection methods all adopt Liquid Chromatography-Tandem Mass Spectrometry (LC-MS/MS) to measure the detection method of benzene azoles mepanipyrim residual quantity in vegetable and fruit, use LC-MS/MS to measure food Residual Pesticides in Farm Produce and have quickly, easy, sensitivity advantages of higher, but due to its price costly, a lot of testing agencies, enterprise or scientific research institutions do not configure this instrument or configuration number of units is less, when adopting LC-MS/MS detection due to different compounds, different mobile phases or chromatographic column need to be used, chromatographic column constantly changed by such needs, mobile phase also expends the long time system is balanced, this constrains the application of LC-MS/MS to a certain extent。Use gas chromatogram tandem mass spectrum (GC-MS/MS) to analyze food Residual Pesticides in Farm Produce and there is the advantages such as quick, easy, highly sensitive, selectivity is strong, the multi-residue analysis of hundreds of kind pesticide can be realized, but have no the report of the GC-MS/MS detection method of benzene azoles mepanipyrim residual quantity in food agricultural product up to now, but have no the report of the GC-MS/MS detection method of benzene azoles mepanipyrim residual quantity in food agricultural product up to now。Additionally, it is known that, QuEChERS pretreatment technology has become sample-pretreating method most widely used in pesticide residue analysis, but QuEChERS method is primarily adapted for use in the High water cut substrate of low-fat content, such as most fruit and vegetable, when in the face of high fat content substrate limited in one's ability, it is generally required to increase normal hexane grease removal, freezing sample extracting solution goes the steps such as fat, but limited efficiency。Some company is proposed enhancement mode lipid and removes patented product-EnhancedMatrixRemoval, EMR-lipid in recent years, is mainly used in removing the lipid chaff interference with straight chain hydrocarbon structure, including free fatty, cholesterol, triglyceride, phospholipid etc.。This product has been made into matrix solid phase dispersion extractant, either directly through dispersive solid-phase extraction flow process, the lipid impurities in extracting solution can be removed after hydroactivated, the present invention applies when this pre-treating method purifies animal derived food and finds, the method is simply efficient, lipid material removal effect is good, sets up the detection method of benzene azoles mepanipyrim residual quantity in the dispersion purification of EMR substrate, gas chromatogram tandem mass spectrum (GC-MS/MS) qualitative and quantitative analysis animal derived food significant。

Summary of the invention

It is an object of the invention to provide the GC-MS/MS rapid assay methods of a kind of benzene azoles mepanipyrim residual quantity, be mainly used in measuring benzene azoles mepanipyrim 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-MS/MS rapid assay methods of a kind of benzene azoles mepanipyrim residual quantity, comprises the steps:

(1) extract

Weigh mixing sample in tool plug centrifuge tube, after adding suitable quantity of water recovery, be quantitatively adding acetonitrile solution homogenizing and extract, be subsequently adding sodium chloride and anhydrous magnesium sulfate, centrifugal after violent vortex 1min。

Purify

Enhancement mode lipid is removed product E MR water activate, pipette sample extracting solution and purify in pipe in the EMR activated, after vortex 1min, 7000r/min is centrifuged 5min, shifts whole supernatant and saltouts to the centrifuge tube equipped with anhydrous magnesium sulfate and sodium chloride, after vortex centrifugal, pipette the supernatant of certain volume, be concentrated into after doing, dissolve constant volume with the acetone that volume ratio is 1/1/normal hexane mixed solvent, after crossing film, treat that gas chromatogram tandem mass spectrum (GC-MS/MS) detects。

(3) preparation of standard working solution

Same kind matrix blank sample without benzene azoles mepanipyrim 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 benzene azoles mepanipyrim series standard working solution of at least 3 concentration。

(4) measure and result calculates

The standard working solution of each Concentraton gradient in step (3) is carried out GC-MS/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-MS/MS to be measured, record the chromatographic peak area of benzene azoles mepanipyrim in sample liquid, substitute into extraction standard working curve, obtaining benzene azoles mepanipyrim content in sample liquid, then the Mass Calculation of sample representated by liquid obtains benzene azoles mepanipyrim residual quantity in sample per sample；If benzene azoles mepanipyrim residual quantity exceedes the range of linearity upper limit in upper machine solution, with constant volume solvent, upper machine solution concentration need to be diluted within the range of linearity。

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 1.2mL/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: 290 DEG C。

In step (4), Mass Spectrometry Conditions is: ionization pattern: electron impact ionization (EI, 70eV)；Ion source temperature 280 DEG C；Collision gas: argon；Multiple-reaction monitoring scan mode MRM, monitoring parameter is:

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 Cereals, animal derived food the benzene azoles qualitative confirmation of mepanipyrim and detection by quantitative in conjunction with GC-MS/MS, average recovery rate is 91.3%～99.0%, average relative standard's deviation (RSD) is 5.2%～8.6%, detection limit, lower than 6.74 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 that our people's food safety and export abroad trade sound development provide strong technical support。

Accompanying drawing explanation

The GC-MS/MS that Fig. 1 is the benzene azoles mepanipyrim mark liquid being added in blank Carnis Sus domestica substrate selects chromatography of ions figure。

The GC-MS/MS that Fig. 2 is the Carnis Sus domestica blank sample without benzene azoles mepanipyrim selects chromatography of ions figure。

The benzene azoles mepanipyrim standard working curve that Fig. 3 is is substrate preparation with the Carnis Sus domestica blank sample without benzene azoles mepanipyrim。

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)；CR21G III centrifuge (Hitachi, Japan)；MS3 basic model vortex mixer (IKA, Germany)；TurboVapLV pattern product automatic concentration instrument (Caliper, USA)；7890N gas chromatogram-5977C mass spectrograph (Agilent, USA)；Enhancement mode lipid is removed product (EnhancedMatrixRemoval, EMR) and is purchased from Anjelen Sci. & Tech. Inc of the U.S.。

Reagent

Acetonitrile, acetone, normal hexane (HPLC level, Merke, Germany)；Anhydrous magnesium sulfate, sodium chloride are analytical pure, all purchased from Chemical Reagent Co., Ltd., Sinopharm Group。

Standard substance: purity 99.0%, purchased from Dr.Ehrenstorfer company of Germany。

Embodiment 1: the detection of benzene azoles mepanipyrim residual quantity in Carnis Sus domestica

(1) sample pre-treatments

Extract

Weigh the 5g Carnis Sus domestica sample through fully mixing 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, after vortex 1min, after the centrifugal 5min of 7000r/min, to be clean。

Purify

Add 4mL water in the purification pipe removing product E MR equipped with enhancement mode lipid, vortex makes it fully activate, pipette 6mL sample extracting solution and purify in pipe in the EMR activated, after vortex 1min, 7000r/min is centrifuged 5min, shift whole supernatant to saltout to the centrifuge tube equipped with anhydrous magnesium sulfate and sodium chloride, after vortex centrifugal, pipette 1mL supernatant, it is concentrated into after doing, dissolve constant volume with the acetone that volume ratio is 1/1/normal hexane mixed solvent, after crossing film, treat that gas chromatogram tandem mass spectrum (GC-MS/MS) detects。

(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 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 that volume ratio is 1/1/normal hexane mixed solvent constant volume；Carnis Sus domestica blank sample without benzene azoles mepanipyrim is processed by above-mentioned pre-treatment step, take 8mL blank extraction and cleaning liquid, it is concentrated into after doing, add acetone/normal hexane mixed solvent vortex that 8mL volume ratio is 1/1 to dissolve, be finally configured to 1,2,5,10,20,50 μ g/L extraction standard working solutions with this solution。

(3) gas chromatogram tandem mass spectrometry (GC-MS/MS) measures

The standard working solution of variable concentrations gradient is injected separately into GC-MS/MS, carries out the quantitative analysis of benzene azoles mepanipyrim 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 working curve；Under the same conditions sample extracting solution is injected GC-MS/MS to be measured, record the chromatographic peak area of benzene azoles mepanipyrim in sample liquid, substitute into standard working curve, obtaining benzene azoles mepanipyrim content in sample liquid, then the Mass Calculation of sample representated by liquid obtains benzene azoles mepanipyrim 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 1.2mL/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: 290 DEG C。

Wherein, mass spectrometry parameters is:

Ionization pattern: electron impact ionization, i.e. EI pattern, energy 70eV。

Ion source temperature: 280 DEG C；Collision gas: argon。

Scan mode: multiple-reaction monitoring (SRM) scan pattern；MRM detects parameter in Table 1。

Table 1: the MRM of embodiment 1 detects parameter

^*For quota ion pair。

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。

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=5721.8X-2777.5, and correlation coefficient is 0.9993。

Recovery of standard addition and repeatability:

Carnis Sus domestica without benzene azoles mepanipyrim adds the benzene azoles mepanipyrim standard solution of 10,20 and 200 g/kg3 concentration levels of μ, 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 1。As can be seen from Table 1, in 3 mark-on levels, the average recovery rate of benzene azoles mepanipyrim is 91.3%～99.0%, and average relative standard's deviation (RSD) is 5.2%～8.6%, illustrates that the response rate of the inventive method is high, reproducible。

The response rate of table 1 benzene azoles mepanipyrim and repeatability (n=6)

Detection limit:

The benzene azoles mepanipyrim extraction standard working solution of variable concentrations is injected GC-MS/MS, calculating detection limit with the cycles of concentration (cycles of concentration of Carnis Sus domestica is for 0.25 times) of 3 times of signal to noise ratios of least concentration extraction standard solution chromatographic peak and sample handling processes, the detection of benzene azoles mepanipyrim is limited to 6.74 μ 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 (3)

1. the GC-MS/MS rapid assay methods of a benzene azoles mepanipyrim residual quantity, it is characterised in that said method comprising the steps of:

(1) extract

Weigh mixing sample in tool plug centrifuge tube, after adding suitable quantity of water, after adding the extraction of acetonitrile solution homogenizing, add sodium chloride and anhydrous magnesium sulfate, centrifugal after violent vortex 1min；

(2) purify

Enhancement mode lipid is removed product E MR water activate, pipette sample extracting solution and purify in pipe in the EMR activated, after vortex 1min, 7000r/min is centrifuged 5min, shifts whole supernatant and saltouts to the centrifuge tube equipped with anhydrous magnesium sulfate and sodium chloride, after vortex centrifugal, pipette the supernatant of certain volume, be concentrated into after doing, dissolve constant volume with the acetone that volume ratio is 1/1/normal hexane mixed solvent, after crossing film, treat that gas chromatogram tandem mass spectrum (GC-MS/MS) detects；

(3) preparation of standard working solution

Same kind matrix blank sample without benzene azoles mepanipyrim 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 benzene azoles mepanipyrim series standard working solution of at least 3 concentration；

(4) measure and result calculates

The standard working solution of each Concentraton gradient in step (3) is carried out GC-MS/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-MS/MS to be measured, record the chromatographic peak area of benzene azoles mepanipyrim in sample liquid, substitute into extraction standard working curve, obtaining benzene azoles mepanipyrim content in sample liquid, then the Mass Calculation of sample representated by liquid obtains benzene azoles mepanipyrim residual quantity in sample per sample；If benzene azoles mepanipyrim residual quantity exceedes the range of linearity upper limit in upper machine solution, with constant volume solvent, upper machine solution concentration need to be diluted within the range of linearity。

2. the GC-MS/MS rapid assay methods of a kind of benzene azoles mepanipyrim residual quantity according to claim 1, it is characterised in that step (1) if in the sample of sample moisture content less, suitable quantity of water must be added before extraction and fully infiltrate。

3. the GC-MS/MS rapid assay methods of a kind of benzene azoles mepanipyrim residual quantity according to claim 1, it is characterized in that, in step (4), GC-MS/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 1.2mL/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: 290 DEG C；Ionization pattern: electron impact ionization (EI, 70eV)；Ion source temperature 280 DEG C；Collision gas: argon；Multiple-reaction monitoring scan mode MRM, monitoring parameter is: