CN117990844A - Method for detecting methiocarb in food - Google Patents
Method for detecting methiocarb in food Download PDFInfo
- Publication number
- CN117990844A CN117990844A CN202410150442.8A CN202410150442A CN117990844A CN 117990844 A CN117990844 A CN 117990844A CN 202410150442 A CN202410150442 A CN 202410150442A CN 117990844 A CN117990844 A CN 117990844A
- Authority
- CN
- China
- Prior art keywords
- sample
- methiocarb
- detecting
- shaking
- food
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000005951 Methiocarb Substances 0.000 title claims abstract description 42
- YFBPRJGDJKVWAH-UHFFFAOYSA-N methiocarb Chemical compound CNC(=O)OC1=CC(C)=C(SC)C(C)=C1 YFBPRJGDJKVWAH-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 27
- 235000013305 food Nutrition 0.000 title claims abstract description 24
- 238000000605 extraction Methods 0.000 claims abstract description 20
- 238000001514 detection method Methods 0.000 claims abstract description 19
- 239000004033 plastic Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- RQBBFKINEJYDOB-UHFFFAOYSA-N acetic acid;acetonitrile Chemical compound CC#N.CC(O)=O RQBBFKINEJYDOB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002347 injection Methods 0.000 claims abstract description 7
- 239000007924 injection Substances 0.000 claims abstract description 7
- 239000006228 supernatant Substances 0.000 claims abstract description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 6
- 229940040526 anhydrous sodium acetate Drugs 0.000 claims abstract description 6
- 230000008014 freezing Effects 0.000 claims abstract description 6
- 238000007710 freezing Methods 0.000 claims abstract description 6
- 238000002791 soaking Methods 0.000 claims abstract description 6
- 238000005303 weighing Methods 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 claims abstract description 5
- 239000012528 membrane Substances 0.000 claims abstract description 4
- 238000005119 centrifugation Methods 0.000 claims abstract description 3
- 239000011159 matrix material Substances 0.000 claims description 30
- 150000002500 ions Chemical class 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 241000209094 Oryza Species 0.000 claims description 18
- 235000007164 Oryza sativa Nutrition 0.000 claims description 18
- 235000009566 rice Nutrition 0.000 claims description 18
- 240000007124 Brassica oleracea Species 0.000 claims description 16
- 235000003899 Brassica oleracea var acephala Nutrition 0.000 claims description 16
- 235000011301 Brassica oleracea var capitata Nutrition 0.000 claims description 16
- 235000001169 Brassica oleracea var oleracea Nutrition 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- 238000001819 mass spectrum Methods 0.000 claims description 9
- 238000012544 monitoring process Methods 0.000 claims description 7
- 238000011084 recovery Methods 0.000 claims description 7
- 239000012086 standard solution Substances 0.000 claims description 6
- 238000004458 analytical method Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000004949 mass spectrometry Methods 0.000 claims description 4
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 235000010149 Brassica rapa subsp chinensis Nutrition 0.000 claims description 3
- 235000000536 Brassica rapa subsp pekinensis Nutrition 0.000 claims description 3
- 241000499436 Brassica rapa subsp. pekinensis Species 0.000 claims description 3
- 238000000889 atomisation Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000010828 elution Methods 0.000 claims description 3
- HJUFTIJOISQSKQ-UHFFFAOYSA-N fenoxycarb Chemical compound C1=CC(OCCNC(=O)OCC)=CC=C1OC1=CC=CC=C1 HJUFTIJOISQSKQ-UHFFFAOYSA-N 0.000 claims description 3
- HQVFCQRVQFYGRJ-UHFFFAOYSA-N formic acid;hydrate Chemical compound O.OC=O HQVFCQRVQFYGRJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 3
- 238000012360 testing method Methods 0.000 claims description 3
- 235000013339 cereals Nutrition 0.000 claims description 2
- 235000021022 fresh fruits Nutrition 0.000 claims description 2
- 235000013311 vegetables Nutrition 0.000 claims description 2
- 235000012055 fruits and vegetables Nutrition 0.000 claims 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 abstract description 9
- 238000004885 tandem mass spectrometry Methods 0.000 abstract description 4
- 238000004445 quantitative analysis Methods 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 238000004451 qualitative analysis Methods 0.000 abstract description 2
- 239000000523 sample Substances 0.000 description 28
- 230000000694 effects Effects 0.000 description 16
- 241000220225 Malus Species 0.000 description 15
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- ZAGNMMRDHSEOPE-UHFFFAOYSA-N (2-chlorophenyl) n-methylcarbamate Chemical compound CNC(=O)OC1=CC=CC=C1Cl ZAGNMMRDHSEOPE-UHFFFAOYSA-N 0.000 description 4
- 239000012491 analyte Substances 0.000 description 4
- 235000021016 apples Nutrition 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- 235000011430 Malus pumila Nutrition 0.000 description 3
- 235000015103 Malus silvestris Nutrition 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000000575 pesticide Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 241000258937 Hemiptera Species 0.000 description 2
- 241000607479 Yersinia pestis Species 0.000 description 2
- 150000001793 charged compounds Chemical class 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 238000002372 labelling Methods 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 241001124076 Aphididae Species 0.000 description 1
- 229940122041 Cholinesterase inhibitor Drugs 0.000 description 1
- 241001583841 Empoasca decipiens Species 0.000 description 1
- 235000016623 Fragaria vesca Nutrition 0.000 description 1
- 240000009088 Fragaria x ananassa Species 0.000 description 1
- 235000011363 Fragaria x ananassa Nutrition 0.000 description 1
- 241001466042 Fulgoromorpha Species 0.000 description 1
- PWWVAXIEGOYWEE-UHFFFAOYSA-N Isophenergan Chemical compound C1=CC=C2N(CC(C)N(C)C)C3=CC=CC=C3SC2=C1 PWWVAXIEGOYWEE-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 241000194622 Tagosodes orizicolus Species 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- XBJFCYDKBDVADW-UHFFFAOYSA-N acetonitrile;formic acid Chemical compound CC#N.OC=O XBJFCYDKBDVADW-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
- 239000000544 cholinesterase inhibitor Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- AJEHNBIPLQJTNU-UHFFFAOYSA-N cyanomethyl acetate Chemical compound CC(=O)OCC#N AJEHNBIPLQJTNU-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229960003910 promethazine Drugs 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000000581 reactive spray deposition Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 239000012224 working solution Substances 0.000 description 1
Landscapes
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention provides a detection method of methiocarb in food, which comprises the steps of weighing a sample into a plastic centrifuge tube, adding water, shaking to completely infiltrate, and soaking; adding acetonitrile-acetic acid extraction solvent into the centrifuge tube in the step S1, oscillating 1 min, adding an extraction bag of anhydrous magnesium sulfate and anhydrous sodium acetate, immediately shaking, oscillating 1 min, putting into a refrigerator, freezing, and taking out for centrifugation; taking supernatant of the centrifuge tube in the step S2, passing through a 0.22 mu m organic filter membrane, transferring into a sample injection vial, and detecting by LC-MS/MS. According to the technical scheme, the acid acetonitrile is used as an extraction solvent to extract the residual of the methiocarb in the food, and the liquid chromatography-triple quadrupole tandem mass spectrometry detection is adopted, so that a detection method for detecting the methiocarb in the food is established, the method is simple and quick, only 10 min is needed for each needle of machine operation, the accuracy is high, and the method is suitable for quick qualitative and quantitative analysis of the methiocarb in the plant-derived food.
Description
Technical Field
The invention relates to the technical field of pesticide detection, in particular to a detection method of methiocarb in food.
Background
Methiocarb (CPMC/Etrofol), the name of which is 2-chlorophenyl N-methylcarbamate, having a molecular formula of C 8H8NClO2, CAS number: 3942-54-9, wherein the pure product is white crystal with a melting point of 90-91 ℃. Has weak phenol smell. Is dissolved in acetone and methanol, slightly dissolved in water, and easily decomposed and failed when meeting alkali. The methiocarb is a cholinesterase inhibitor, has rapid action and short residual effect period, and does not influence the use effect due to temperature; the pesticide is mainly used for preventing and controlling pests such as rice leafhoppers, cotton leafhoppers, rice planthoppers, aphids, scale insects on fruit trees, whiteflies and the like.
Currently, detection methods of the methiocarb are mainly gas chromatography tandem mass spectrometry and liquid chromatography. When the gas chromatography tandem mass spectrometry is adopted for detection, the sample solution generally needs to undergo complicated purification steps to reduce the pollution to an instrument system, the instrument operation time of each needle of the method is relatively long, and the research also finds that the response stability of the methiocarb on the gas chromatography tandem mass spectrometer is poor, the influence of a matrix is larger, and the method accuracy is poor; the liquid chromatography is detected by an ultraviolet detector, the method has poor specificity/selectivity, is easy to be interfered by a matrix, is inaccurate in qualitative and quantitative, has lower sensitivity, needs a purification and concentration step in pretreatment, and has long time consumption and low efficiency in the detection process. Therefore, the technical aim of the patent is to provide a detection method for detecting the harmful promethazine in the plant-derived food by adopting a high performance liquid chromatography-tandem mass spectrometry detection method, which has important significance for research on the pesticide metabolism mechanism and food safety analysis and monitoring.
Disclosure of Invention
In order to make up for the defects of the prior art, the invention provides a detection method of the methiocarb in food.
The invention is realized by the following technical scheme: a detection method of the methiocarb in food comprises the following specific steps:
S1 preparation of a sample: weighing a sample into a plastic centrifuge tube, adding water, shaking to completely infiltrate, and soaking;
S2, extracting a sample: adding acetonitrile-acetic acid extraction solvent into the centrifuge tube in the step S1, oscillating 1 min, adding an extraction bag of anhydrous magnesium sulfate and anhydrous sodium acetate, immediately shaking, oscillating 1 min, putting into a refrigerator, freezing, and taking out for centrifugation;
S3, detection of a sample: taking supernatant of the centrifuge tube obtained in the step S2, passing through a 0.22 mu m organic filter membrane, transferring into a sample injection vial, and detecting by LC-MS/MS;
s4, instrument conditions of a liquid chromatograph-triple quadrupole mass spectrometer: the chromatographic conditions are a chromatographic column AGILENT ECLIPSE Plus RRHD C, 18 column 100 mm ×2.1mm, 2.1 μm; column temperature 40 ℃, sample injection quantity 1 [ mu ] L, flow rate: 0.3 mL/min; mobile phase: a is 20 mu mol/L methylene diphosphate-5 mmol/L ammonium acetate-0.1% formic acid-water solution; b is methanol; gradient elution procedure ：0～0.6 min,90%A;0.6～2.0 min,90%A～50%A;2.0～5.0 min,50%A～35%A;5.0～5.5 min,35%A～0%A;5.5～7.5 min,0%A;7.5～7.6 min,0%A～90%A;7.6～10.0 min,90%A;
The mass spectrum condition is an electrospray positive ion mode, the capillary voltage is 3000V, the atomization air pressure is 35 to psi, the temperature of the drying air is 250 ℃, the temperature of the sheath air is 350 ℃, and the dry air flow is 15 to L/min, and the monitoring mode is a multi-reaction monitoring mode;
MRM mass spectrometry parameters of S5 methiocarb: the parent ion of sulfenamide is m/z 186, the child ion is m/z 129 and m/z94, the optimal collision energy of the child ion m/z 112.4 is 10 eV, and the optimal collision energy of the child ion m/z94 is 40 eV.
As a preferred scheme, the specific steps of the step S2 are adding 10mL acetonitrile-acetic acid 99+1, v/v extraction solvent, oscillating 1 min, adding an extraction bag containing 4 g anhydrous magnesium sulfate and 1.5 g anhydrous sodium acetate, immediately shaking, oscillating 1 min, putting in a refrigerator, freezing at-20 ℃ for 2 hours, taking out and centrifuging 10min at a rotating speed of 8500 r/min.
Further, the sample in the step S1 is the grain after being homogenized, specifically, the step is to accurately weigh 2 g samples into a 50 mL plastic centrifuge tube, add 10 mL water, shake to completely soak, and soak for 2 hours.
Further, the sample in step S1 is homogenized rice.
Further, the sample in the step S1 is a homogenized fresh fruit and vegetable, and the specific steps are that accurately weighing a 2g sample into a 50mL plastic centrifuge tube, adding 10mL water, shaking to completely infiltrate, and soaking for 2 hours.
Further, the sample in step S1 is homogenized apple or cabbage.
Further, the method also comprises a step S6, wherein the supernatant in the step S3 is used as a matrix solution, 1,2, 5, 10, 25 and 50 mug/L are prepared by using the matrix solution of which the sample is rice, or 5, 10, 50, 200 and 250 mug/L are prepared by using the matrix solution of which the sample is apple or Chinese cabbage, the method is carried out on-machine analysis, the peak area is taken as an ordinate y, the mass concentration is taken as an abscissa x, and a matrix matching standard curve is drawn.
Further, the method also comprises a step S7 of a labeling experiment, wherein the specific steps are that 10, 50 and 200 mug/kg standard solutions are respectively added into blank matrixes of rice, apples and cabbages, the concentration of each addition is measured in parallel for 6 times, and the labeling recovery rate experiment is carried out according to the operation of the steps S1-S5.
The invention adopts the technical proposal, and compared with the prior art, the invention has the following beneficial effects: the invention uses acid acetonitrile as an extraction solvent to extract the residue of the methiocarb in the food, adopts liquid chromatography-triple quadrupole tandem mass spectrometry detection, establishes a detection method for detecting the methiocarb in the food, is simple and quick, only needs 10min per needle of machine operation, has high accuracy, and is suitable for quick qualitative and quantitative analysis of the methiocarb in plant-derived food.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 is a molecular structural formula of methiocarb;
FIG. 2 is a first-order mass spectrum of the methiocarb;
fig. 3 is a second-order mass spectrum of the methiocarb at collision energy ce=10 ev;
Fig. 4 is a second-order mass spectrum of the methiocarb at collision energy ce=20 ev;
Fig. 5 is a second-order mass spectrum of the methiocarb at collision energy ce=30 ev;
fig. 6 is a second-order mass spectrum of the methiocarb at collision energy ce=40 ev;
FIG. 7 is a diagram of a possible cleavage process of methiocarb on LCMS;
FIG. 8 is a 10 μg/L chromatogram of a solvent standard;
FIG. 9 is a chromatogram of a rice blank sample;
FIG. 10 is a chromatogram of a rice blank labeled 10 μg/kg;
FIG. 11 is a chromatogram of an apple blank;
FIG. 12 is a chromatogram of an apple blank labeled 10 μg/kg;
FIG. 13 is a chromatogram of a cabbage blank;
FIG. 14 is a chromatogram of a cabbage blank labeled 10 μg/kg;
Detailed Description
In order that the above-recited objects, features and advantages of the present application will be more clearly understood, a more particular description of the application will be rendered by reference to the appended drawings and appended detailed description. It should be noted that, without conflict, the embodiments of the present application and features in the embodiments may be combined with each other.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced otherwise than as described herein, and therefore the scope of the present invention is not limited to the specific embodiments disclosed below.
The method for detecting methiocarb in food according to the embodiment of the present invention will be specifically described with reference to fig. 1 to 11.
Instrument, reagents used in the examples:
LC-MS Agilent 1290 II 6495C (Agilent, USA); two-bit electronic level (Mettler Toledo company, switzerland); tissue grinder (2010 Geno/Grinder cube, SPEX samplePrep, USA); vortex mixer (IKA company, germany); centrifuges (thermo fisher, usa); 50 mL and 15 mL with plug centrifuge tube; disposable nylon needle filter.
The standards of methiocarb (100 mg/L) were purchased from Alta. Acetonitrile, methanol, chromatographic grade; acetic acid, formic acid, ammonium acetate, analytically pure;
Standard working fluid (1 mg/L): 0.1 mL standard stock solution (100 mg/L) was removed into a 10mL volumetric flask, diluted with methanol to a standard working solution with a mass concentration of 1 mg/L and stored at-4℃protected from light.
Example 1
S1 preparation of a sample: the sample is homogenized rice, 2 g samples (accurate to 0.01 g) are accurately weighed into a 50 mL plastic centrifuge tube, 10 mL water is added, and the mixture is shaken to be fully soaked for 2 hours;
S2, extracting a sample: adding 10mL acetonitrile-acetic acid (99+1, v/v) extraction solvent into the centrifuge tube of the step S1, oscillating 1 min, adding an extraction bag containing 4g anhydrous magnesium sulfate and 1.5 g anhydrous sodium acetate, immediately shaking, oscillating 1 min, placing in a refrigerator (-20 ℃) for freezing for 2 hours, taking out and centrifuging 10 min at a rotating speed of 8500 r/min;
S3, detection of a sample: taking supernatant of the centrifuge tube obtained in the step S2, passing through a 0.22 mu m organic filter membrane, transferring into a sample injection vial, and detecting by LC-MS/MS;
s4, instrument conditions of a liquid chromatograph-triple quadrupole mass spectrometer: the chromatographic conditions are a chromatographic column AGILENT ECLIPSE Plus RRHD C, 18 column 100 mm ×2.1mm, 2.1 μm; column temperature 40 ℃, sample injection quantity 1 [ mu ] L, flow rate: 0.3 mL/min; mobile phase: a is 20 mu mol/L methylene diphosphate-5 mmol/L ammonium acetate-0.1% formic acid-water solution; b is methanol; gradient elution procedure ：0～0.6 min,90%A;0.6～2.0 min,90%A～50%A;2.0～5.0 min,50%A～35%A;5.0～5.5 min,35%A～0%A;5.5～7.5 min,0%A;7.5～7.6 min,0%A～90%A;7.6～10.0 min,90%A;
The mass spectrum condition is electrospray positive ion mode, capillary voltage is 3000V, atomization pressure is 35: 35 psi, drying gas temperature is 250 ℃, sheath gas temperature is 350 ℃, drying gas flow is 15: 15L/min, and the monitoring mode is multi-reaction monitoring (MRM) mode;
MRM mass spectrometry parameters of S5 methiocarb: the parent ion of sulfenamide is m/z 186, the child ion is m/z 129 and m/z94, the optimal collision energy of the child ion m/z 112.4 is 10 eV, and the optimal collision energy of the child ion m/z94 is 40 eV.
TABLE 1 MRM Mass Spectrometry parameters for Miao Wei
Example 2
S1 preparation of a sample: the sample was a homogenized apple and 10g samples (accurate to 0.01 g) were accurately weighed into 50mL plastic centrifuge tubes.
Other conditions were the same as in example 1.
Example 3
S1 preparation of a sample: the sample is homogenized cabbage, and 10g samples (accurate to 0.01 g) are accurately weighed into a 50mL plastic centrifuge tube.
Other conditions were the same as in example 1.
Example 4
The rice, apple and cabbage samples are extracted and purified according to the steps S1-S2. Sample extraction is carried out according to the test method of the steps S1-S2, the supernatant in the step S3 is used as matrix solution, 1,2, 5, 10, 25 and 50 mug/L are prepared by using the matrix solution of which the sample is rice, or 5, 10, 50, 200 and 250 mug/L are prepared by using the matrix solution of which the sample is apple or Chinese cabbage, and the matrix matching standard curve is drawn by using the peak area as an ordinate y and the mass concentration as an abscissa x through on-machine analysis.
Example 5
And (3) marking: standard solutions with the levels of 10, 50 and 200 mug/kg are respectively added into blank matrixes of paddy, strawberry and cabbage, the concentration of each addition is measured for 6 times in parallel, and the standard adding recovery rate test is carried out according to the operation of the steps S1-S5.
Results and discussion
1. Instrument method for establishing pest-killing
The molecular formula of the methiocarb is C 8H8NClO2, the precise molecular mass is 185.0244, and the primary amine group is contained in the molecular structural formula, so that scanning is performed in a positive ion full scanning mode to obtain a molecular ion peak [ M+H ] - M/z 186 and a source internal cleavage Jie Suipian peak [ M-CH3-NH-CO+H ] - M/z129 (figure 2). Since the response of the molecular ion peak [ M+H ] - M/z 186 is higher, the M/z 186 is selected as a parent ion for sub-ion scanning, the collision energy is respectively set to 10, 20, 30 and 40 eV, a secondary mass spectrum (shown in figures 3-6) is obtained, fragment ions M/z129, M/z94, M/z 93 and M/z 65 are obtained, and by comparison, two fragment ions M/z129 and M/z94 with higher response are selected as sub-ions. By optimizing the collision energy of the two sub-ions, the optimum collision energy of the sub-ion m/z129 is 12 eV, and the optimum collision energy of the ion m/z94 is 35 eV.
2. Establishes a pretreatment method of the methiocarb in plant-derived foods such as rice, apples, cabbages and the like.
According to the invention, 1% acetonitrile formate and 1% acetonitrile acetate are selected as extraction reagents, and as a result, the recovery rate of the target substances of the two reagents is found to be 80% -120%, which indicates that the two extraction reagents can meet the requirements, and the invention prefers 1% acetic acid-acetonitrile as the extraction reagent.
3. Establishes a quantitative detection method of the methiocarb
The Matrix Effect (ME) of methiocarb in rice, apples and cabbages was evaluated. The matrix effect refers to the inhibition or enhancement of the signal generated by ionization of components other than the target compound in the sample during analysis of the target compound. Matrix effect= (area of analyte in matrix matching standard/area of analyte in solvent standard x 100%), matrix effect is negligible when ME is 80% -120%, ME is less than 80%, matrix inhibition effect, ME is greater than 120%, matrix enhancement effect.
The results show that the matrix effects of the pest carbofuran in the rice, the apple and the cabbage are 376.5%, 202.8% and 216.8%, respectively, and the matrix enhancement effect is shown, which shows that the presence of matrix impurities in the extraction solution is helpful for improving the sensitivity of the analyte, but the quantitative accuracy of the positive result is also influenced by the matrix effect, and in order to eliminate the influence of the matrix effect, the patent adopts a matrix matching correction standard quantitative method.
4. Working curve and quantitative limit
The rice, apple and cabbage samples were extracted and purified according to part 2.3. Sample extraction is carried out according to a 2.3 part test method to obtain a matrix solution, the matrix solution is prepared into series standard solutions of 1,2, 5, 10, 25 and 50 mug/L (rice) or 5, 10, 50, 200 and 250 mug/L (apple and cabbage), the series standard solutions are analyzed by a machine, the peak area is taken as an ordinate (y), the mass concentration is taken as an abscissa (x), a matrix matching standard curve is drawn, and the correlation coefficient r 2 is more than 0.99. The standard adding of the three matrixes is 0.01 mg/kg, the signal to noise ratio (S/N) is more than or equal to 10, and the requirement of quantitative limit is met. The linear equation, linear range, correlation coefficient and method quantification are shown in Table 2.
TABLE 2 Linear equation, linear range, correlation coefficient and quantitative limit for methiocarb
5. Method specificity
As can be seen from rice, apple and cabbage chromatograms, no interference peak appears at the peak position of the methiocarb, which indicates that the chromatographic conditions have good selectivity and specificity.
6. Residual effect
The residue effect (Carryover effects) of the compound on the chromatographic column is examined experimentally, and the result shows that the compound has almost no residue effect and does not affect the samples of the subsequent operation.
7. Accuracy and precision: standard solutions with the levels of 10, 50 and 200 mug/kg are respectively added into blank matrixes of rice, apples and cabbages, the concentration of each addition is measured for 6 times in parallel, and a standard recovery rate test is carried out. The average recovery rate of the analyte is 85.7% -101.6%; the Relative Standard Deviation (RSDs) is 0.8% -3.9%; meanwhile, the quantitative limit is set to 10 mug/kg, which meets the requirements of accuracy and precision.
Table 3 normalized recovery and relative standard deviation of methiocarb in three matrices (n=6)
In the description of the present specification, the terms "one embodiment," "some embodiments," "particular embodiments," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. The detection method of the methiocarb in the food is characterized by comprising the following specific steps of:
S1 preparation of a sample: weighing a sample into a plastic centrifuge tube, adding water, shaking to completely infiltrate, and soaking;
S2, extracting a sample: adding acetonitrile-acetic acid extraction solvent into the centrifuge tube in the step S1, oscillating 1 min, adding an extraction bag of anhydrous magnesium sulfate and anhydrous sodium acetate, immediately shaking, oscillating 1 min, putting into a refrigerator, freezing, and taking out for centrifugation;
S3, detection of a sample: taking supernatant of the centrifuge tube obtained in the step S2, passing through a 0.22 mu m organic filter membrane, transferring into a sample injection vial, and detecting by LC-MS/MS;
S4, instrument conditions of a liquid chromatograph-triple quadrupole mass spectrometer: the chromatographic conditions are a chromatographic column AGILENT ECLIPSE Plus RRHD C, 18 column 100 mm ×2.1, mm, 2.1 μm; column temperature 40 ℃, sample injection quantity 1[ mu ] L, flow rate: 0.3 mL/min; mobile phase: a is 20 mu mol/L methylene diphosphate-5 mmol/L ammonium acetate-0.1% formic acid-water solution; b is methanol; gradient elution procedure ：0～0.6 min,90%A;0.6～2.0 min,90%A～50%A;2.0～5.0 min,50%A～35%A;5.0～5.5 min,35%A～0%A;5.5～7.5 min,0%A;7.5～7.6 min,0%A～90%A;7.6～10.0 min,90%A;
The mass spectrum condition is an electrospray positive ion mode, the capillary voltage is 3000V, the atomization air pressure is 35 to psi, the temperature of the drying air is 250 ℃, the temperature of the sheath air is 350 ℃, and the dry air flow is 15 to L/min, and the monitoring mode is a multi-reaction monitoring mode;
MRM mass spectrometry parameters of S5 methiocarb: the parent ion of sulfenamide is m/z 186, the child ion is m/z 129 and m/z 94, the optimal collision energy of the child ion m/z 112.4 is 10 eV, and the optimal collision energy of the child ion m/z 94 is 40 eV.
2. The method for detecting the methiocarb in the food according to claim 1, wherein the specific step of the step S2 is adding 10mL acetonitrile-acetic acid 99+1, v/v extraction solvent, shaking 1 min, adding an extraction bag containing 4g anhydrous magnesium sulfate and 1.5 g anhydrous sodium acetate, immediately shaking, shaking 1 min, freezing in a refrigerator at-20 ℃ for 2 hours, taking out and centrifuging 10min at a rotational speed of 8500 r/min.
3. The method for detecting the methiocarb in the food according to claim 2, wherein the sample in the step S1 is a homogenized grain, and the specific steps are accurately weighing a 2g sample into a 50 mL plastic centrifuge tube, adding 10 mL water, shaking to completely infiltrate, and soaking for 2 hours.
4. A method for detecting methiocarb in food according to claim 3, wherein the sample in step S1 is homogenized rice.
5. The method for detecting the methiocarb in the food according to claim 2, wherein the sample in the step S1 is a homogenized fresh fruit and vegetable, and the specific steps are that accurately weighing a 2g sample into a 50mL plastic centrifuge tube, adding 10 mL water, shaking to completely soak the fruit and vegetable, and soaking the fruit and vegetable for 2 hours.
6. The method for detecting the methiocarb in the food according to claim 5, wherein the sample in the step S1 is homogenized apple or cabbage.
7. The method for detecting the methiocarb in the food according to claim 4 or 6, further comprising the step of S6, wherein the supernatant in the step of S3 is used as a matrix solution, 1,2,5, 10, 25 and 50 mug/L are prepared by using the matrix solution of which the sample is rice, or 5, 10, 50, 200 and 250 mug/L are prepared by using the matrix solution of which the sample is apple or Chinese cabbage, and the method is carried out by performing on-machine analysis, wherein the peak area is taken as an ordinate y, the mass concentration is taken as an abscissa x, and a matrix matching standard curve is drawn.
8. The method for detecting sulfenamide in foods according to claim 4 or 6, further comprising a step S7 of adding standard solutions with the levels of 10, 50 and 200 mug/kg to blank matrixes of paddy, apple and cabbage respectively, wherein each adding concentration is measured in parallel for 6 times, and the standard adding recovery rate test is carried out according to the operation of steps S1-S5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410150442.8A CN117990844A (en) | 2024-02-02 | 2024-02-02 | Method for detecting methiocarb in food |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410150442.8A CN117990844A (en) | 2024-02-02 | 2024-02-02 | Method for detecting methiocarb in food |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117990844A true CN117990844A (en) | 2024-05-07 |
Family
ID=90899011
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410150442.8A Pending CN117990844A (en) | 2024-02-02 | 2024-02-02 | Method for detecting methiocarb in food |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117990844A (en) |
-
2024
- 2024-02-02 CN CN202410150442.8A patent/CN117990844A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4709016A (en) | Molecular analytical release tags and their use in chemical analysis | |
| CN108398498B (en) | Rapid quantitative analysis method for four bisphenol compounds in common food | |
| Lu et al. | Quantitative analysis of mitragynine in human urine by high performance liquid chromatography-tandem mass spectrometry | |
| CN111289637B (en) | Method for detecting patulin in apple juice | |
| CN113049719A (en) | Method and kit for detecting free testosterone | |
| CN115184497B (en) | Method for determining content of 2, 4-epibrassinolide in dendrobium candidum | |
| CN108414664A (en) | A kind of method that ultra high efficiency conjunction phase chromatography-tandem mass spectrum technology splits, measures Chiral pesticide isopropyl methoxalamine enantiomer | |
| CN110243920B (en) | Method for detecting small molecular sugar by using 2-hydrazine quinoline as reactive matrix in MALDI-TOF-MS | |
| CN109828051B (en) | Method for detecting toxic compound | |
| CN110441453A (en) | A kind of method of separation detection phosphamidon isomers | |
| Wang et al. | Derivatization of 5-fluorouracil with 4-bromomethyl-7-methoxycoumarin for determination by liquid chromatography-mass spectrometry | |
| CN108508130B (en) | Method for splitting and measuring enantiomers of chiral pesticides metalaxyl and dimethomorph by ultra-high performance combined chromatography-tandem mass spectrometry technology | |
| CN117990844A (en) | Method for detecting methiocarb in food | |
| Becker et al. | Quantitative determination of ceftiofur-related residues in bovine raw milk by LC-MS/MS with electrospray ionization | |
| Bruenner et al. | Simultaneous determination of multiple aldehydes in biological tissues and fluids using gas chromatography/stable isotope dilution mass spectrometry | |
| Clouette et al. | Confirmation of 11-nor-Δ9-tetrahydrocannabinol in urine as its t-butyldimethylsilyl derivative using GC/MS | |
| Clatworthy et al. | Gas chromatographic-mass spectrometric confirmation of radioimmunoassay results for cannabinoids in blood and urine | |
| CN117368342A (en) | Method for detecting sulfenamide in food | |
| CN111307992B (en) | Pre-column derivative liquid chromatography-mass spectrometry analysis method for quantitatively detecting organic acid in PM2.5 | |
| CN110286177B (en) | Method for detecting barbaloin | |
| Wang et al. | A novel and sensitive screening method for β-agonists in porcine urine by using atmospheric solid analysis probe source coupled tandem mass spectrometry | |
| CN108398506B (en) | Method for splitting and measuring enantiomers of chiral pesticides quizalofop-ethyl and fluazifop-p-butyl by ultra-high performance combined chromatography-tandem mass spectrometry technology | |
| CN111337611A (en) | Method for detecting malachite green, leucomalachite green, crystal violet and leucocyte crystal violet in aquatic products | |
| Yoon et al. | Mass spectrometry of methyl and methyl-d3 derivatives of diuretic agents | |
| CN111272939A (en) | Method for determining penicillic acid content in fruits |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |