CN105758968B - The LC MS MS detection methods of mandipropamid residual quantity in a kind of vegetables and dry fruit - Google Patents

The LC MS MS detection methods of mandipropamid residual quantity in a kind of vegetables and dry fruit Download PDF

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CN105758968B
CN105758968B CN201610259450.1A CN201610259450A CN105758968B CN 105758968 B CN105758968 B CN 105758968B CN 201610259450 A CN201610259450 A CN 201610259450A CN 105758968 B CN105758968 B CN 105758968B
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sample
mandipropamid
liquid
vegetables
standard
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CN105758968A (en
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李慧冬
陈子雷
董崭
范文静
张文君
朱倩
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Institute of Agricultural Quality Standards and Testing Technology of Shandong Academy of Agricultural Sciences
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Institute of Agricultural Quality Standards and Testing Technology of Shandong Academy of Agricultural Sciences
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • 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
    • G01N30/02—Column chromatography
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • 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
    • G01N30/02—Column chromatography
    • G01N2030/022—Column chromatography characterised by the kind of separation mechanism
    • G01N2030/027—Liquid chromatography

Abstract

The invention discloses a kind of LC MS MS detection methods of mandipropamid residual quantity in vegetables and dry fruit, belong to pesticide residue determination technical field.This method extracts the mandipropamid remained in sample, after extract solution is dispersed through purification, Liquid Chromatography-Tandem Mass Spectrometry with acetonitrile solution homogeneous（LC‑MS‑MS）Detection, the standard curve of correction, quantified by external standard method are established using the vehicle solution without agricultural chemicals to be measured.This method average recovery rate is 85.0%~94.6%, average relative standard's deviation（RSD）For 0.86%~2.89%%, detection limit 0.003mg/kg of the present invention, quantitative detection limit 0.01mg/kg.With easy to operate, quick, high sensitivity, it is reproducible, qualitative, quantitative is accurate the advantages of." uniform limit " technical requirements of 0.01mg/kg residue limits can be met, strong technical support is provided to ensure that our people's food security, export abroad trade develop in a healthy way.

Description

The LC-MS-MS detection methods of mandipropamid residual quantity in a kind of vegetables and dry fruit
Technical field
The present invention relates to a kind of detection method of mandipropamid residual quantity, relate more specifically in a kind of vegetables and dry fruit The LC-MS-MS of mandipropamid residual quantity（Liquid chromatography-tandem mass spectrometry）Detection method, belong to pesticide residue determination technology Field.
Background technology
Mandipropamid chemical name is 2- (4- chlorphenyls)-N- [2- (3- methoxyl group -4- Propargyls epoxides-benzene Base)-ethyl] -2- propyl-s 2- alkynyloxy groups-acetamide, English language Chemical entitled 2- (4-chlorophenyl)-N- [2- (3- methoxy-4-prop-2-ynyloxy-phenyl) -ethyl]-2-prop-2-ynyloxy-acetamide.CAS accession number For [374726-62-2].Molecular formula：C23H22ClNO4, relative molecular mass：411.9.Chemical structural formula is as follows：
Physicochemical property：Light brown powder, 96.4 DEG C ~ 97.3 DEG C of fusing point.About 200 DEG C of boiling point starts to thermally decompose.Vapour pressure< 9.4×10-7 Pa(25℃).Determination of oil-water partition coefficient log Pow：3.2℃(25℃).The mg/L of solubility 4.2 (25 DEG C) in water. Mammalian toxicity：Rat acute LD5>5000 mg/kg, rat acute LD50>2000 mg/kg, rat acute Suck LC50>5000 mg/kg, lagophthalmos eyeball have minimal irritation, and rabbit skin has moderate stimulation, by rat test without mutagenesis, Teratogenesis, carcinogenesis, also impassivity murder by poisoning, the breeding on rat quickly can absorb and discharge without influence, big metabolism in mice.It is raw State toxicity：Birds acute oral Bobwhite LD50>5000 mg/kg, rainbow trout LC50>2.9 mg/L.Honeybee tags and orally LD50>200 mg/, earthworm LC50>1000mg/kg.Environment degradable effect：It is stable in the aqueous solution of pH4 ~ 9.Photodissociation in water The d of DT50 1.7 (pH=7,25 DEG C).The mL/g of soil metabolism Koc 847 (mL/g of scope 405 ~ 1294).Soil degrading DT50 17 D (d of scope 2 ~ 29).
Mandipropamid has greater activity to the sprouting for suppressing spore.It also suppresses mycelial growth and spore simultaneously Formation, to target pathogen, mandipropamid is preferably used as preventative sprinkling, but treatment can also be provided in incubation period Effect.Mandipropamid has very high affinity to the wax coat of plant surface.When be sprayed onto plant surface and precipitation drying Afterwards, most of active component is adsorbed by wax layer, and is difficult to be fallen by rain-out.Sub-fraction active component penetrates into plant In tissue, because itself activity is high, this part being absorbed into plant tissue is enough to suppress mycelial growth, so as to protect Whole blade is protected not by disease infestation.These properties ensure its stability and high efficiency, and lasting period length, action effect is good, and dosage is low Have a wide range of application.
With concern of the people to Pesticide Residues toxicity, the detection of mandipropamid residual is also taken seriously.According to The United States Federal's publication message, Environmental Protection Agency's issue on March 28th, 2016 regulations, revises mandipropamid （mandipropamid）MRL.Potato（Wet skin）Middle limitation is less than 0.15ppm；Stem tuber and corm kind vegetables are (sub- Group 1C) limiting the quantity is less than 0.09ppm.Meanwhile if European Union, Japan and other countries regulation field as China main exit market make Do not registered with agricultural chemicals in the country, when not formulating corresponding residue limits standard, be exported to its national food agricultural product Residue limits carry out 0.01mg/L " uniform limit " in animal derived food including livestock meat etc..
GB2763-2014 of the newest promulgation in China《Pesticide MRL》Define zoxamide, cyanato- 7 kinds of amine, Boscalid, fluopicolide, fenhexamid, thifluzamide, mandipropamid new acid amide fungicides are in food Residue limits, and at present there has been no the report of this 7 kinds of new type bactericide residue analysis methods is analyzed simultaneously, therefore establish fruits and vegetables In simple accurately new acid amide fungicides residue analysis method be extremely urgent.
Open report mainly has immunoassay, gas-chromatography on new acid amide fungicides analysis means both at home and abroad Method, liquid chromatography, gas chromatography-mass spectrography, wherein reporting that more analysis method is gas chromatography-mass spectrography at present Method.And more mandipropamid residuals are detected in the complex various vegetables of matrix and dry fruit using LC-MS method, and And wide adaptation range, high sensitivity, reproducible, there is not been reported for the accurate LC-MS-MS methods of qualitative, quantitative.
Therefore, a kind of easy, quick, high sensitivity, reproducible, the accurate mandipropamid of qualitative, quantitative in vegetables and Method for detecting residue in dry fruit urgently develops.
The content of the invention
In place of overcoming above-mentioned the deficiencies in the prior art, and provide a kind of easy, quick, sensitivity The detection method of mandipropamid residual quantity in high, reproducible, the accurate vegetables dry fruit of qualitative, quantitative.
To realize object above, the technical solution adopted in the present invention is：Mandipropamid remains in a kind of vegetables dry fruit The LC-MS-MS of amount（Liquid chromatography-tandem mass spectrometry）Detection method, comprise the following steps：
（1）It is prepared by sample：
Market is gathered into sample according to quartering division to 500g, this sample is divided into two parts of 2 × 200g, uses food processing Machine crushes, in the closed preservation of -20 DEG C of refrigerator-freezers.
（2）Extraction and purification：
Weigh 5.0g and prepared sample in 50 mL centrifuge tubes, add 10ml acetonitriles, high-speed homogenization 2min, add 2g NaCl, acutely shake 1min.Take upper strata acetonitrile mutually to centrifuge, take 1mL supernatants to add 1mL methanol and water mixed solution（Volume Than 1:1）0.2 μm of nylon micro porous filter membrane is crossed, obtained liquid phase part is testing sample.
（3）The preparation of standard working solution:
Same species matrix blank sample without mandipropamid is handled by above-mentioned steps (1), (2), obtains sample extraction Scavenging solution, the mandipropamid series hybrid standard working solution of at least five concentration is configured to blank extraction and cleaning liquid.
（4）Measure and result calculate:
The standard working solution of each concentration gradient in step (3) is subjected to LC-MS-MS measure, with the color of standard working solution Spectral peak area carries out regression analysis to its respective concentration, obtains standard working curve；It will be purified under the same conditions in step (2) Sample liquid afterwards carries out LC-MS-MS measure, measures the chromatographic peak area of mandipropamid in sample liquid, substitutes into standard curve, obtains The mandipropamid amine content into sample liquid, then the Mass Calculation of sample according to representated by sample liquid obtain mandipropamid in sample Amine residual quantity.
Sample need to reduce sample weighting amount, and add suitable quantity of water fully to infiltrate if dehydrated vegetables and dry fruit in step (1).
When being extracted in step (2) with acetonitrile add sodium chloride saltout need to be added when the less sample of water content is saltoutd it is a certain amount of Water.
The mobile phase of liquid chromatogram described in step (4) includes A phases and B phases, and A phases are methanol, and B phases are water；Flow velocity： 0.3mL/min；Sampling volume：1.0μL；Column oven：45℃.
The method that liquid chromatogram uses gradient elution in step (4), gradient elution program are：
Chromatographic column ZORBAX ECLIPSE the Plus C18,2.1 × 50mm, 1.8 μm of liquid chromatogram in step (4).
Analysis condition is in step (4)：375 DEG C of ion guns of ion source temperature:ESI. electron spray voltage：5000V.Atomization Device pressure：0.138MPa.Auxiliary heating gas：0.379MPa.Scan mode：Cation scans.
Mass Spectrometer Method uses multiple-reaction monitoring (MRM) anion scan pattern in step (4), mandipropamid it is female from Son, daughter ion, go cluster voltage and the collision energy to be respectively：
The parent ion and daughter ion pair of the detection filtrate Pesticides in step (4), if its chromatography of ions peak retention time It is consistent with standard working solution；And in filtrate (sample) two daughter ions of target compound relative abundance it is suitable with concentration When the ion relative abundance deviation of bare substrate standard liquid is no more than 30%, then judge this kind of agricultural chemicals in the sample be present；If Above-mentioned two condition can not meet simultaneously, then judge to be free of this kind of agricultural chemicals.
Beneficial effect possessed by the present invention：
1st, the present invention uses LC-MS-MS（Liquid chromatography-tandem mass spectrometry）It is legal quantitative determination Residues in Vegetables and Pleocidin content, using quantified by external standard method, average recovery rate is 85.0%~94.6%, average relative standard's deviation（RSD）For 0.86%~2.89%%, it is high sensitivity, reproducible.
2nd, detection limit 0.003mg/kg of the present invention, quantitative detection limit 0.01mg/kg, being capable of easy, quick, qualitative, quantitative standard Mandipropamid residual quantity in true vegetables dry fruit, the country such as the U.S., Japan, European Union can be met to corresponding food safety detection The technical requirements of 0.01mg/kg residue limits, i.e. " uniform limit ", will be to ensure our people's food security and export abroad Trade, which develops in a healthy way, provides strong technical support.
3rd, sample-pretreating method that is easy, quick and can effectively avoiding sample mesostroma from disturbing is established, will be located before this Reason method combination LC-MS-MS（Liquid chromatography-tandem mass spectrometry）Applied to the qualitative confirmation of mandipropamid in vegetables, dry fruit food product With quantitative detection.
Brief description of the drawings
Fig. 1 mandipropamid standard curves；
Fig. 2 mandipropamid standard specimen 0.2mg/L chromatograms；
Fig. 3 tomato blank chromatograms；
Fig. 4 tomatoes add 0.1mg/kg chromatograms；
Fig. 5 chilli blank chromatograms；
Fig. 6 chilli adds 0.1mg/kg chromatograms
Fig. 7 raisins blank chromatograms；
Fig. 8 raisins add 0.1mg/kg chromatograms.
Specific embodiment
The following example is the further explanation to invention, but the present invention is not limited only to this.
The instrument used in embodiment：
LC-MS instrument：Agilent 6460 Triple Quad LC/MS；Type gas-chromatography-the TSQ of Trace 1310 8000 type triple quadrupole bar tandem mass spectrometers（Thermo companies of the U.S.)；Sartorius electronic balances（One thousandth, Beijing match More Li Si balances Co., Ltds)；IKA T18 Basic homogenizers（German IKA companies)；The basic model turbine mixers of MS 3 （IKA, Germany）.
Medicine and standard items：(mass concentration is equal purchased from environmental quality supervision and inspection center of the Tianjin Ministry of Agriculture for standard items For 100ug/mL).Acetonitrile (HPLC levels, Merke, Germany)；Formic acid (HPLC levels, CNW, Germany)；Methanol, sodium chloride It is pure to analyze, it is purchased from Chemical Reagent Co., Ltd., Sinopharm Group.
Matrix matching standard liquid：The matrix mixed standard solution of various concentrations is made into blank sample matrix solution, is used In making standard working curve, different types of matrix correction work solution, matrix matching is made in variety classes vegetables or dry fruit Standard liquid is now with the current.
For trying vegetables dry fruit：Tomato, chilli and raisins are purchased from local supermarket.
The LC-MS-MS detections of mandipropamid residual quantity in the tomato of embodiment 1：
（1）It is prepared by sample：
Tomato sample will be gathered according to quartering division to 500g, this sample is divided into two parts of 2 × 200g, uses food processing Machine crushes, in the closed preservation of -20 DEG C of refrigerator-freezers.
（2）Extraction and purification：
Tomato sample that 5.0g has been prepared is weighed in 50 mL centrifuge tubes, adds 10ml acetonitriles, high-speed homogenization 2min, 2g NaCl are added, acutely shake 1min.Take upper strata acetonitrile mutually to centrifuge, take 1mL supernatants addition 1mL first alcohol and water mixing molten Liquid（Volume ratio 1:1）0.2 μm of nylon micro porous filter membrane is crossed, obtained liquid phase part is testing sample.
（3）The preparation of standard working solution:
Tomato matrix blank sample without mandipropamid is handled by above-mentioned steps (1), (2), it is net to obtain sample extraction Change liquid, worked with blank extraction and cleaning liquid preparation 0.01,0.02,0.05,0.1,0.2,0.5mg/L mandipropamids standard molten Liquid, standard working solution is entered into LC-MS/MS analyses, regression analysis is carried out to its respective concentration with gained peak area, with sample introduction concentration （mg/L）For abscissa, peak area is ordinate, obtains standard working curve.
（4）Measure and result calculate:
The standard working solution of each concentration gradient in step (3) is subjected to LC-MS-MS measure, with the color of standard working solution Spectral peak area carries out regression analysis to its respective concentration, obtains standard working curve；It will be purified under the same conditions in step (2) Sample liquid injection LC-MS-MS afterwards is measured, and measures the chromatographic peak area of mandipropamid in sample liquid, it is bent to substitute into standard Line, mandipropamid amine content in sample liquid is obtained, then the Mass Calculation of sample according to representated by sample liquid obtains double in sample Mandipropamid residual quantity.
The mobile phase of liquid chromatogram described in step (4) includes A phases and B phases, and A phases are methanol, and B phases are water；Flow velocity： 0.3mL/min；Sampling volume：1.0μL；Column oven：45℃.
The method that liquid chromatogram uses gradient elution in step (4), gradient elution program such as table 1：
Table 1：The gradient elution program of embodiment 1
Chromatographic column ZORBAX ECLIPSE the Plus C18,2.1 × 50mm, 1.8 μm of liquid chromatogram in step (4).
Analysis condition is in step (4)：375 DEG C of ion guns of ion source temperature:ESI. electron spray voltage：5000V.Atomization Device pressure：0.138MPa.Auxiliary heating gas：0.379MPa.Scan mode：Cation scans.
Mass Spectrometer Method uses multiple-reaction monitoring (MRM) anion scan pattern in step (4), mandipropamid it is female from Son, daughter ion, go cluster voltage and collision energy respectively such as table 2：
Table 2：The MRM detection parameters of embodiment 1
The parent ion and daughter ion pair of the detection filtrate Pesticides in step (4), if its chromatography of ions peak retention time It is consistent with standard working solution；And in filtrate (sample) two daughter ions of target compound relative abundance it is suitable with concentration When the ion relative abundance deviation of bare substrate standard liquid is no more than 30%, then judge this kind of agricultural chemicals in the sample be present；If Above-mentioned two condition can not meet simultaneously, then judge to be free of this kind of agricultural chemicals.
Regression analysis is carried out to its respective concentration with the chromatographic peak area of standard working solution, obtains standard working curve.
The standard curve of mandipropamid in the tomato bare substrate of table 3
Recovery of standard addition and repeatability：
Adding for mg/kg3 concentration of 0.01mg/kg, 0.1mg/kg and 0..5 is added in the apple without mandipropamid Add level, the determination of residual amount is carried out by above-mentioned processing step after agricultural chemicals adds 30min.By measure concentration and the theoretical addition of agricultural chemicals Concentration is compared, and obtains agricultural chemicals TIANZHU XINGNAO Capsul, each pitch-based sphere parallel determination 6 times, is obtained its relative standard deviation, is determined It the results are shown in Table 4.As can be seen from Table 4, in 3 mark-on levels, the average recovery rate of mandipropamid for 93.1%~ 94.5%, average relative standard's deviation (RSD) is 0.86%~2.89%, illustrates that the rate of recovery of the inventive method is higher, is repeated Property is good.
The rate of recovery of mandipropamid and repeatability (n=6) in the embodiment 1 of table 4
Detection limit：The mandipropamid extraction standard working solution of various concentrations is injected into LC-MS-MS, with least concentration The cycles of concentration of 3 times of signal to noise ratio of extraction standard solution chromatographic peak and sample handling processes calculates detection limit, the inspection of mandipropamid Rising limit is 3 μ g/kg.
The LC-MS-MS detections of mandipropamid residual quantity in the chilli of embodiment 2：
（1）It is prepared by sample：
By the chilli sample of collection according to quartering division to 500g, this sample is divided into two parts of 2 × 200g, uses food Processing machine crushes, in the closed preservation of -20 DEG C of refrigerator-freezers.
（2）Extraction and purification：
Chilli sample that 5.0g has been prepared is weighed in 50 mL centrifuge tubes, adds 10ml acetonitriles, high-speed homogenization 2min, 2g NaCl are added, acutely shake 1min.Take upper strata acetonitrile mutually to centrifuge, take 1mL supernatants to add 1mL first alcohol and water and mix Close solution（Volume ratio 1:1）0.2 μm of nylon micro porous filter membrane is crossed, obtained liquid phase part is testing sample.
（3）The preparation of standard working solution:
Chilli matrix blank sample without mandipropamid is handled by above-mentioned steps (1), (2), obtains sample extraction Scavenging solution, worked with blank extraction and cleaning liquid preparation 0.01,0.02,0.05,0.1,0.2,0.5mg/L mandipropamids standard molten Liquid, standard working solution is entered into LC-MS/MS analyses, regression analysis is carried out to its respective concentration with gained peak area, with sample introduction concentration （mg/L）For abscissa, peak area is ordinate, obtains standard working curve.
The preparation of standard working solution, liquid chromatogram-tandem mass spectrometry (LC-MS-MS) determine and the operation of Qualitative Identification Step, chromatogram and Mass Spectrometry Conditions are consistent with the measure of mandipropamid in the tomato sample of embodiment 1.
Recovery of standard addition and repeatability：
0.01mg/kg, 0.1mg/kg and 0.5 mg/kg3 concentration are added in the chilli without mandipropamid Pitch-based sphere, the determination of residual amount is carried out by above-mentioned processing step after agricultural chemicals adds 30min.Measure concentration is added with agricultural chemicals theory Add concentration to be compared, obtain agricultural chemicals TIANZHU XINGNAO Capsul, each pitch-based sphere parallel determination 6 times, obtain its relative standard deviation, survey Surely 5 be the results are shown in Table.As can be seen from Table 5, in 3 mark-on levels, the average recovery rate of mandipropamid for 85.0%~ 86.6%, average relative standard's deviation (RSD) is 2.32%~2.45%, illustrates that the rate of recovery of the inventive method is higher, is repeated Property is good.
The rate of recovery of mandipropamid and repeatability (n=6) in the embodiment 2 of table 5
Detection limit：The mandipropamid extraction standard working solution of various concentrations is injected into LC-MS-MS, with least concentration The cycles of concentration of 3 times of signal to noise ratio of extraction standard solution chromatographic peak and sample handling processes calculates detection limit, the inspection of mandipropamid Rising limit is 3 μ g/kg.
Apply the LC-MS-MS detections of mandipropamid residual quantity in the raisins of example 3：
（1）It is prepared by sample：
By the grape dry-eye disease of collection according to quartering division to 500g, this sample is divided into two parts of 2 × 200g, uses food Processing machine crushes, in the closed preservation of -20 DEG C of refrigerator-freezers.
（2）Extraction and purification：
Grape dry sample that 5.0g has been prepared is weighed in 50 mL centrifuge tubes, adds 10ml acetonitriles, high-speed homogenization 2min, 2g NaCl are added, acutely shake 1min.Take upper strata acetonitrile mutually to centrifuge, take 1mL supernatants to add 1mL first alcohol and water and mix Close solution（Volume ratio 1:1）0.2 μm of nylon micro porous filter membrane is crossed, obtained liquid phase part is testing sample.
（3）The preparation of standard working solution:
Raisins matrix blank sample without mandipropamid is handled by above-mentioned steps (1), (2), obtains sample extraction Scavenging solution, worked with blank extraction and cleaning liquid preparation 0.01,0.02,0.05,0.1,0.2,0.5mg/L mandipropamids standard molten Liquid, standard working solution is entered into LC-MS/MS analyses, regression analysis is carried out to its respective concentration with gained peak area, with sample introduction concentration （mg/L）For abscissa, peak area is ordinate, obtains standard working curve.
The preparation of standard working solution, Liquid Chromatography-Tandem Mass Spectrometry (LC-MS-MS) determine and the operation of Qualitative Identification Step, chromatogram and Mass Spectrometry Conditions are consistent with the measure of mandipropamid in tomato sample in embodiment 1.
Recovery of standard addition and repeatability：
0.01mg/kg, 0.1mg/kg and 0.5 mg/kg3 concentration are added in the raisins without mandipropamid Pitch-based sphere, the determination of residual amount is carried out by above-mentioned processing step after agricultural chemicals adds 30min.Measure concentration is added with agricultural chemicals theory Add concentration to be compared, obtain agricultural chemicals TIANZHU XINGNAO Capsul, each pitch-based sphere parallel determination 6 times, obtain its relative standard deviation, survey Surely 6 be the results are shown in Table.As can be seen from Table 6, in 3 mark-on levels, the average recovery rate of mandipropamid for 87.2%~ 94.6%, average relative standard's deviation (RSD) is 1.56%~2.20%, illustrates that the rate of recovery of the inventive method is higher, is repeated Property is good.
The rate of recovery of mandipropamid and repeatability (n=6) in the embodiment 3 of table 6
Detection limit：The mandipropamid extraction standard working solution of various concentrations is injected into LC-MS-MS, with least concentration The cycles of concentration of 3 times of signal to noise ratio of extraction standard solution chromatographic peak and sample handling processes calculates detection limit, the inspection of mandipropamid Rising limit is 3 μ g/kg.
As shown by data, by embodiment method preparation 0.01,0.02,0.05,0.1,0.2,0.5mg/L mandipropamid standards Working solution, with sample introduction concentration（mg/L）For abscissa, peak area is ordinate, draws standard curve.In 0.001 ~ 0.1mg/L In the range of peak area and sample introduction concentration be in good linear relationship, calibration curve equation is：Y=187579x-107.43, phase relation Number is r=0.9973.
Above-described embodiment is only that the preferred embodiment of the present invention is described, and not the scope of the present invention is limited Fixed, on the premise of design spirit of the present invention is not departed from, this area ordinary skill technology is made to technical scheme All variations and modifications, it all should fall into the protection domain of claims of the present invention determination.

Claims (4)

  1. A kind of 1. LC-MS-MS detection methods of mandipropamid residual quantity in vegetables and dry fruit, it is characterised in that methods described Comprise the following steps：1）It is prepared by sample：Sample will be gathered according to quartering division, crushed with food processor, in -20 DEG C of refrigerator-freezers Closed preservation；2）Extraction and purification：Weigh and prepared sample in centrifuge tube, add acetonitrile, NaCl is added after high-speed homogenization, Acutely shaking 1min；Take upper strata acetonitrile mutually to centrifuge, take supernatant to add volume ratio 1:1 methanol and water mixed solution cross 0.2 μm of Buddhist nun Imperial micropore filtering film, obtained liquid phase part are testing sample；3）The preparation of standard working solution：Mandipropamid will be free of Same species matrix blank sample press above-mentioned steps 1), 2) handle, obtain sample extraction scavenging solution, with blank extraction and cleaning liquid prepare Into the mandipropamid series hybrid standard working solution of at least five concentration；4）Measure and result calculate：Will be each dense in step 3) The standard working solution for spending gradient carries out LC-MS-MS measure, and its respective concentration is returned with the chromatographic peak area of standard working solution Return analysis, obtain standard working curve；The sample liquid after being purified in step 2) is subjected to LC-MS-MS measure under the same conditions, The chromatographic peak area of mandipropamid in sample liquid is measured, standard curve is substituted into, obtains mandipropamid amine content in sample liquid, so The Mass Calculation of sample according to representated by sample liquid obtains mandipropamid residual quantity in sample afterwards；
    Step 2), which is extracted and weighs 5.0g in purifying, has prepared sample in 50 mL centrifuge tubes, adds 10ml acetonitriles, high speed is even 2min is starched, 2g NaCl is added, acutely shakes 1min；Take upper strata acetonitrile mutually to centrifuge, take 1mL supernatants to add 1mL volume ratio 1: 1 methanol and water mixed solution cross 0.2 μm of nylon micro porous filter membrane, and obtained liquid phase part is testing sample；
    Step 4) determines includes A phases and B phases, A with the mobile phase of liquid chromatogram in the LC-MS-MS measure described in result calculating It is mutually methanol, B phases are water；Flow velocity：0.3mL/min；Sampling volume：1.0μL；Column oven：45℃；
    The method that liquid chromatogram uses gradient elution in LC-MS-MS measure described in step 4), gradient elution program are：
    ；
    The chromatographic column ZORBAX ECLIPSE Plus C18 of liquid chromatogram in LC-MS-MS measure described in step 4), 2.1 × 50mm, 1.8 μm；
    Mass Spectrometer Method uses multiple-reaction monitoring (MRM) scan pattern, mandipropamid in LC-MS-MS measure described in step 4) Parent ion, the daughter ion of amine, go cluster voltage and the collision energy to be respectively：
  2. 2. the LC-MS-MS detection methods of mandipropamid residual quantity in a kind of vegetables according to claim 1 and dry fruit, It is characterized in that：This sample is divided into 2 × 200g two by sample according to quartering division to 500g in the preparation of step 1) sample Part, crushed with food processor, in the closed preservation of -20 DEG C of refrigerator-freezers.
  3. 3. the LC-MS-MS detection methods of mandipropamid residual quantity in a kind of vegetables according to claim 1 and dry fruit, Characterized in that, analysis condition is during the LC-MS-MS described in step 4) is determined：Ion source temperature：375℃；Ion gun： ESI；Electron spray voltage：5000V；Nebulizer pressure：0.138MPa；Auxiliary heating gas：0.379MPa；Scan mode：Cation Scanning.
  4. 4. the LC-MS-MS detection methods of mandipropamid residual quantity in a kind of vegetables according to claim 1 and dry fruit, Characterized in that, sample need to reduce sample weighting amount, and add suitable quantity of water fully to infiltrate if dehydrated vegetables and dry fruit in step 1).
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