CN102183611B - Method for detecting pesticide residue in white paeony root crude drug - Google Patents
Method for detecting pesticide residue in white paeony root crude drug Download PDFInfo
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- CN102183611B CN102183611B CN 201110059067 CN201110059067A CN102183611B CN 102183611 B CN102183611 B CN 102183611B CN 201110059067 CN201110059067 CN 201110059067 CN 201110059067 A CN201110059067 A CN 201110059067A CN 102183611 B CN102183611 B CN 102183611B
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- crude drug
- paeony root
- white paeony
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- pesticide residue
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- 235000006484 Paeonia officinalis Nutrition 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000003814 drug Substances 0.000 title claims abstract description 15
- 239000000447 pesticide residue Substances 0.000 title claims abstract description 15
- 229940079593 drug Drugs 0.000 title claims abstract description 14
- 241001106477 Paeoniaceae Species 0.000 title claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 238000001514 detection method Methods 0.000 claims abstract description 7
- 239000000284 extract 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
- 238000001819 mass spectrum Methods 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 150000002500 ions Chemical class 0.000 claims description 16
- 241000894006 Bacteria Species 0.000 claims description 12
- 239000003905 agrochemical Substances 0.000 claims description 11
- 238000004458 analytical method Methods 0.000 claims description 10
- 239000006228 supernatant Substances 0.000 claims description 10
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 claims description 8
- 229940124530 sulfonamide Drugs 0.000 claims description 8
- 244000236658 Paeonia lactiflora Species 0.000 claims description 7
- 235000008598 Paeonia lactiflora Nutrition 0.000 claims description 7
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical class [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 6
- NWWZPOKUUAIXIW-DHZHZOJOSA-N (E)-thiamethoxam Chemical compound [O-][N+](=O)/N=C/1N(C)COCN\1CC1=CN=C(Cl)S1 NWWZPOKUUAIXIW-DHZHZOJOSA-N 0.000 claims description 4
- PXMNMQRDXWABCY-UHFFFAOYSA-N 1-(4-chlorophenyl)-4,4-dimethyl-3-(1H-1,2,4-triazol-1-ylmethyl)pentan-3-ol Chemical compound C1=NC=NN1CC(O)(C(C)(C)C)CCC1=CC=C(Cl)C=C1 PXMNMQRDXWABCY-UHFFFAOYSA-N 0.000 claims description 4
- TWFZGCMQGLPBSX-UHFFFAOYSA-N Carbendazim Natural products C1=CC=C2NC(NC(=O)OC)=NC2=C1 TWFZGCMQGLPBSX-UHFFFAOYSA-N 0.000 claims description 4
- 206010011224 Cough Diseases 0.000 claims description 4
- 239000005760 Difenoconazole Substances 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- 239000005784 Fluoxastrobin Substances 0.000 claims description 4
- 239000005906 Imidacloprid Substances 0.000 claims description 4
- WXZVAROIGSFCFJ-UHFFFAOYSA-N N,N-diethyl-2-(naphthalen-1-yloxy)propanamide Chemical compound C1=CC=C2C(OC(C)C(=O)N(CC)CC)=CC=CC2=C1 WXZVAROIGSFCFJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005585 Napropamide Substances 0.000 claims description 4
- 239000005924 Pirimiphos-methyl Substances 0.000 claims description 4
- 239000005925 Pymetrozine Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005839 Tebuconazole Substances 0.000 claims description 4
- 239000005842 Thiophanate-methyl Substances 0.000 claims description 4
- VXSIXFKKSNGRRO-MXOVTSAMSA-N [(1s)-2-methyl-4-oxo-3-[(2z)-penta-2,4-dienyl]cyclopent-2-en-1-yl] (1r,3r)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carboxylate;[(1s)-2-methyl-4-oxo-3-[(2z)-penta-2,4-dienyl]cyclopent-2-en-1-yl] (1r,3r)-3-[(e)-3-methoxy-2-methyl-3-oxoprop-1-enyl Chemical class CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)O[C@@H]1C(C)=C(C\C=C/C=C)C(=O)C1.CC1(C)[C@H](/C=C(\C)C(=O)OC)[C@H]1C(=O)O[C@@H]1C(C)=C(C\C=C/C=C)C(=O)C1 VXSIXFKKSNGRRO-MXOVTSAMSA-N 0.000 claims description 4
- 150000003851 azoles Chemical class 0.000 claims description 4
- 239000006013 carbendazim Substances 0.000 claims description 4
- JNPZQRQPIHJYNM-UHFFFAOYSA-N carbendazim Chemical compound C1=C[CH]C2=NC(NC(=O)OC)=NC2=C1 JNPZQRQPIHJYNM-UHFFFAOYSA-N 0.000 claims description 4
- FHIVAFMUCKRCQO-UHFFFAOYSA-N diazinon Chemical compound CCOP(=S)(OCC)OC1=CC(C)=NC(C(C)C)=N1 FHIVAFMUCKRCQO-UHFFFAOYSA-N 0.000 claims description 4
- BQYJATMQXGBDHF-UHFFFAOYSA-N difenoconazole Chemical compound O1C(C)COC1(C=1C(=CC(OC=2C=CC(Cl)=CC=2)=CC=1)Cl)CN1N=CN=C1 BQYJATMQXGBDHF-UHFFFAOYSA-N 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- UFEODZBUAFNAEU-NLRVBDNBSA-N fluoxastrobin Chemical compound C=1C=CC=C(OC=2C(=C(OC=3C(=CC=CC=3)Cl)N=CN=2)F)C=1C(=N/OC)\C1=NOCCO1 UFEODZBUAFNAEU-NLRVBDNBSA-N 0.000 claims description 4
- YWTYJOPNNQFBPC-UHFFFAOYSA-N imidacloprid Chemical compound [O-][N+](=O)\N=C1/NCCN1CC1=CC=C(Cl)N=C1 YWTYJOPNNQFBPC-UHFFFAOYSA-N 0.000 claims description 4
- 229940056881 imidacloprid Drugs 0.000 claims description 4
- NNKVPIKMPCQWCG-UHFFFAOYSA-N methamidophos Chemical compound COP(N)(=O)SC NNKVPIKMPCQWCG-UHFFFAOYSA-N 0.000 claims description 4
- MEBQXILRKZHVCX-UHFFFAOYSA-N methidathion Chemical compound COC1=NN(CSP(=S)(OC)OC)C(=O)S1 MEBQXILRKZHVCX-UHFFFAOYSA-N 0.000 claims description 4
- IOUNQDKNJZEDEP-UHFFFAOYSA-N phosalone Chemical compound C1=C(Cl)C=C2OC(=O)N(CSP(=S)(OCC)OCC)C2=C1 IOUNQDKNJZEDEP-UHFFFAOYSA-N 0.000 claims description 4
- QHOQHJPRIBSPCY-UHFFFAOYSA-N pirimiphos-methyl Chemical group CCN(CC)C1=NC(C)=CC(OP(=S)(OC)OC)=N1 QHOQHJPRIBSPCY-UHFFFAOYSA-N 0.000 claims description 4
- QXJKBPAVAHBARF-BETUJISGSA-N procymidone Chemical compound O=C([C@]1(C)C[C@@]1(C1=O)C)N1C1=CC(Cl)=CC(Cl)=C1 QXJKBPAVAHBARF-BETUJISGSA-N 0.000 claims description 4
- QHMTXANCGGJZRX-WUXMJOGZSA-N pymetrozine Chemical compound C1C(C)=NNC(=O)N1\N=C\C1=CC=CN=C1 QHMTXANCGGJZRX-WUXMJOGZSA-N 0.000 claims description 4
- HYJYGLGUBUDSLJ-UHFFFAOYSA-N pyrethrin Natural products CCC(=O)OC1CC(=C)C2CC3OC3(C)C2C2OC(=O)C(=C)C12 HYJYGLGUBUDSLJ-UHFFFAOYSA-N 0.000 claims description 4
- 229940070846 pyrethrins Drugs 0.000 claims description 4
- 239000002728 pyrethroid Substances 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- QGHREAKMXXNCOA-UHFFFAOYSA-N thiophanate-methyl Chemical group COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC QGHREAKMXXNCOA-UHFFFAOYSA-N 0.000 claims description 4
- HYVWIQDYBVKITD-UHFFFAOYSA-N tolylfluanid Chemical compound CN(C)S(=O)(=O)N(SC(F)(Cl)Cl)C1=CC=C(C)C=C1 HYVWIQDYBVKITD-UHFFFAOYSA-N 0.000 claims description 4
- FFSJPOPLSWBGQY-UHFFFAOYSA-N triazol-4-one Chemical compound O=C1C=NN=N1 FFSJPOPLSWBGQY-UHFFFAOYSA-N 0.000 claims description 4
- RROQIUMZODEXOR-UHFFFAOYSA-N triforine Chemical compound O=CNC(C(Cl)(Cl)Cl)N1CCN(C(NC=O)C(Cl)(Cl)Cl)CC1 RROQIUMZODEXOR-UHFFFAOYSA-N 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 238000000889 atomisation Methods 0.000 claims description 3
- 238000000132 electrospray ionisation Methods 0.000 claims description 3
- 238000011067 equilibration Methods 0.000 claims description 3
- 239000012634 fragment Substances 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims description 3
- -1 polypropylene Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 abstract description 7
- 125000001477 organic nitrogen group Chemical group 0.000 abstract description 5
- 239000000843 powder Substances 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 3
- 239000002274 desiccant Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- CFNHVUGPXZUTRR-UHFFFAOYSA-N n'-propylethane-1,2-diamine Chemical compound CCCNCCN CFNHVUGPXZUTRR-UHFFFAOYSA-N 0.000 abstract 1
- 230000010355 oscillation Effects 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 239000012629 purifying agent Substances 0.000 abstract 1
- 241000736199 Paeonia Species 0.000 description 10
- 239000000575 pesticide Substances 0.000 description 8
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
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- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003987 organophosphate pesticide Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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Abstract
The invention provides a method for detecting pesticide residue in a white paeony root crude drug, comprising the following steps of: extracting powder of the white paeony root crude drug with acetonitril in oscillation, then, performing dispersed purification by using N-propyl ethylene diamine as a dispersion purifying agent and using anhydrous magnesium sulfate as a drying agent; evaporating solvent of the extract to dry at 40 DEG C in a rotary evaporators; and taking liquid chromatogram as a separation means and taking mass spectrum as a detection means after dissolving the residual again. The method provided by the invention can simultaneously detect 23 kinds of pesticide residues of organic chloride, organic phosphor and organic nitrogen types. By using the method provided by the invention to analyze the pesticide residue in the white paeony root crude drug, the sample is simply and conveniently processed, rate of recovery is high, and universality is high, so that the method has better application prospect.
Description
Technical field
The invention belongs to Chinese crude drug limits of harmful substances detection technique field, relate to the detection method of traditional Chinese medicinal material samples Pesticide Residues, be specifically related to a kind of method that detects simultaneously 23 kinds of residues of pesticides in the white Peony Root.
Background technology
Problems of Drug Safety is directly connected to the people's livelihood, for reducing the Chinese crude drug Pesticide Residues, improves China's tcm product competitive power in the international market, and the Detecting Pesticide analysis is a very important part.The root of herbaceous peony is as China's conventional Chinese medicine, and it is necessary that it is carried out the Detecting Pesticide analysis, and root of herbaceous peony Sample Pretreatment Technique Used commonly used mainly is the solid phase extraction techniques take Florisil, neutral alumina, silica gel or ketjenblack EC as filler at present.Solid phase extraction techniques needs a large amount of solvents carry out post activation and drip washing, and environmental pollution is large, and is more time-consuming and impurity is more, and the agricultural chemicals recovery is not high.In addition, existing root of herbaceous peony pesticide residues method mainly is gas chromatography-electron capture detection method or gas chromatography-flame photometric detection method, and vapor-phase chromatography is not suitable for detection involatile, thermal instability agricultural chemicals.And existing method has only detected organochlorine, organophosphorus pesticide, and universality is not good enough.
Summary of the invention
The present invention is directed to the deficiency that above-mentioned prior art exists, a kind of method that detects pesticide residue in white paeony root crude drug is provided, is a kind of method that can measure simultaneously 23 kinds of organochlorines, organophosphorus and organic nitrogen pesticide residues in the root of herbaceous peony sample.
For achieving the above object, the technology used in the present invention means are: take acetonitrile as extracting solvent, N-propyl group ethylenediamine (PSA) as disperseing cleanser, anhydrous magnesium sulfate as drying agent, the white Peony Root powder is carried out extraction and cleaning process; The employing liquid chromatography is separation means; Detecting device is selected highly versatile, highly sensitive mass detector.May further comprise the steps:
1, sample pretreatment
(1) extract: behind root of herbaceous peony sample crushing screening, accurately weighed a certain amount of root of herbaceous peony sample powder adds acetonitrile and extracts in centrifuge tube, merges extract;
(2) purify: in extract, add a certain amount of PSA and anhydrous magnesium sulfate, vortex mixed, centrifugal, get supernatant, evaporate to dryness, residue add the methyl alcohol dissolving, and be centrifugal;
2, liquid chromatography-mass spectrography is measured
(1) liquid phase chromatogram condition: chromatographic column Agilent ZORBAX SB-C
18(4.6 mm * 250 mm, 5 μ m); Mobile phase A: contain 20% methanol-water solution of 5 mmol/L ammonium formates, Mobile phase B: contain the methanol solution of 5 mmol/L ammonium formates, elution program is as follows: 0-5 min, 26%B ~ 52%B; 5 ~ 15 min, 52% B ~ 70%B; 15 ~ 45 min, 70% B ~ 83%B; 45 ~ 46 min, 83% B ~ 100%B; 46 ~ 65 min, 100% B; Analysis times 65 min, equilibration time 20 min.Flow velocity: 0.5 mL/min, column temperature: 20 ℃, sample size: 20 μ L;
(2) mass spectrum condition: electro-spray ionization, positive ion SIM mode detection, fragment voltage 100 V; Atomization gas pressure 40 psi; Dry gas flow velocity 11 L/min; 350 ° of C of dry gas temperature; Capillary voltage 3500 V.
Agricultural chemicals of the present invention relates to 23 kinds of organochlorines, organophosphorus and organic nitrogen agricultural chemicals, is respectively: acephatemet, pymetrozine, Diacloden, Imidacloprid, pyridine worm miaow, carbendazim, thiophanate methyl, triforine, methidathion, Fluoxastrobin, cough up bacterium piperazine, triazolone, procymidone, napropamide, Tolylfluanid, Tebuconazole, diazinon, phonetic bacterium sulfanilamide (SN), zolone, pirimiphos-methyl, Difenoconazole, pyrethrins, fluorine bacterium azoles.
The invention provides that a kind of simple and convenient sample treatment, the recovery are high, universality is strong and can measure simultaneously the method for 23 kinds of organochlorines, organophosphorus and organic nitrogen residues of pesticides in the white Peony Root.The inventive method has good repeatability (＜11%) and the recovery (20 agricultural chemicals are all at 70-120%, and 3 agricultural chemicals are below reaching about 60%), detects and is limited to 0.767-11.5 μ g/Kg.
Description of drawings
Total ion current (TIC) chromatogram of 23 kinds of standard sample of pesticide mixed solutions of Fig. 1 and selection chromatography of ions figure.
Fig. 2 adds total ion current (TIC) chromatogram and the selection chromatography of ions figure of the pesticide residue in white paeony root crude drug analysis of 23 kinds of agricultural chemicals.
Total ion current (TIC) chromatogram that Fig. 3 pesticide residue in white paeony root crude drug is analyzed and selection chromatography of ions figure.
Embodiment
The invention will be further described below in conjunction with drawings and Examples.
Embodiment 1
Using liquid chromatography-mass spectrography analyzes 23 kinds of organochlorines, organophosphorus and organic nitrogen agricultural chemicals.
The standard solution preparation: it is an amount of to get respectively each standard sample of pesticide, accurately weighed, dissolves with methyl alcohol.As the standard items stock solution.The standard solution of low concentration is by obtaining with an amount of methyl alcohol dilution stock solution.
Liquid phase chromatogram condition: Agilent ZORBAX SB-C18 (4.6 mm * 250 mm, 5 μ m); Mobile phase A: contain 20% methanol-water solution of 5 mmol/L ammonium formates, Mobile phase B: contain the methanol solution of 5 mmol/L ammonium formates, elution program is as follows: 0-5 min, 26%B ~ 52%B; 5 ~ 15 min, 52% B ~ 70%B; 15 ~ 45 min, 70% B ~ 83%B; 45 ~ 46 min, 83% B ~ 100%B; 46 ~ 65 min, 100% B; Analysis times 65 min, equilibration time 20 min.Flow velocity: 0.5 mL/min, column temperature: 20 ℃, sample size: 20 μ L.
The mass spectrum condition: electro-spray ionization, positive ion SIM mode detection, the m/z value is as shown in table 1; Fragment voltage 100 V; Atomization gas pressure 40 psi; Dry gas flow velocity 11 L/min; 350 ° of C of dry gas temperature; Capillary voltage 3500 V.
The total ions chromatogram of 23 kinds of standard sample of pesticide mixed solutions and selection chromatography of ions figure see accompanying drawing 1, among the figure: 1: acephatemet; 2: Diacloden; 3: pymetrozine; 4: Imidacloprid; 5: pyridine worm miaow; 6: carbendazim; 7: thiophanate methyl; 8: triforine; 9: methidathion; 10: Fluoxastrobin; 11: cough up the bacterium piperazine; 12: triazolone; 13: procymidone; 14: napropamide; 15: Tolylfluanid; 16: Tebuconazole; 17: diazinon; 18: phonetic bacterium sulfanilamide (SN); 19: zolone; 20: pirimiphos-methyl; 21: Difenoconazole; 22: pyrethrins; 23: fluorine bacterium azoles.
The m/z of table 1 SIM ion and corresponding pesticide name thereof
Embodiment 2
Using liquid chromatography-mass spectrography analyzes the white Peony Root that adds 23 kinds of agricultural chemicals.
Sample pretreatment: root of herbaceous peony sample is pulverized, after crossing the sieve of aperture 200 μ m, get 5.0 g root of herbaceous peony sample powder, accurately weighed in 50 mL Corning polypropylene centrifuge tubes, add and mix reference substance solution 0.5 mL, add again 20 mL acetonitriles, vortex mixed 1 min, leave standstill 20 min, 20 ℃ of lower centrifugal 10 min of 4000 r/min get supernatant; Add again 10 mL acetonitriles to centrifuge tube, repeat aforesaid operations 1 time.Merge extracted twice liquid, add 60 mg PSA and 180 mg anhydrous magnesium sulfates, vortex mixed 1 min, 20 ℃ of lower centrifugal 10 min of 4000 r/min, get supernatant, in 40 ℃ of lower Rotary Evaporators evaporates to dryness of using, the accurate 0.5 mL methyl alcohol that adds of residue dissolves, centrifugal, get supernatant, stand-by.
Sample analysis: adopt embodiment 1 same chromatogram, mass spectrum condition to analyze, the total ions chromatogram and the selection chromatography of ions figure that add the pesticide residue in white paeony root crude drug analysis of 23 kinds of agricultural chemicals see Fig. 2.Among Fig. 2: 1: acephatemet; 2: Diacloden; 3: pymetrozine; 4: Imidacloprid; 5: pyridine worm miaow; 6: carbendazim; 7: thiophanate methyl; 8: triforine; 9: methidathion; 10: Fluoxastrobin; 11: cough up the bacterium piperazine; 12: triazolone; 13: procymidone; 14: napropamide; 15: Tolylfluanid; 16: Tebuconazole; 17: diazinon; 18: phonetic bacterium sulfanilamide (SN); 19: zolone; 20: pirimiphos-methyl; 21: Difenoconazole; 22: pyrethrins; 23: fluorine bacterium azoles.
Embodiment 3
Using liquid chromatography-mass spectrography analyzes white Peony Root.
Sample pretreatment: root of herbaceous peony sample is pulverized, after crossing the sieve of aperture 200 μ m, get 5.0 g root of herbaceous peony sample powder, accurately weighed in 50 mL Corning polypropylene centrifuge tubes, add 20 mL acetonitriles, vortex mixed 1 min leaves standstill 20 min, 20 ℃ of lower centrifugal 10 min of 4000 r/min get supernatant; Add again 10 mL acetonitriles to centrifuge tube, repeat aforesaid operations 1 time.Merge extracted twice liquid, add 60 mg PSA and 180 mg anhydrous magnesium sulfates, vortex mixed 1 min, 20 ℃ of lower centrifugal 10 min of 4000 r/min, get supernatant, in 40 ℃ of lower Rotary Evaporators evaporates to dryness of using, the accurate 0.5 mL methyl alcohol that adds of residue dissolves, centrifugal, get supernatant, stand-by.
Sample analysis: adopt embodiment 1 same chromatogram, mass spectrum condition to analyze, the total ions chromatogram of pesticide residue in white paeony root crude drug analysis and selection chromatography of ions figure see Fig. 3.
Claims (1)
1. method that detects pesticide residue in white paeony root crude drug is characterized in that realizing by following steps:
(1) sample pretreatment
Extract: white Peony Root is pulverized, excessively behind the sieve of aperture 200 μ m, got 5.0 g White Peony Roots, accurately weighedly in 50 mL Corning polypropylene centrifuge tubes, add 20 mL acetonitriles, vortex mixed 1 min, leave standstill 20 min, 20 ℃ of lower centrifugal 10 min of 4000 r/min get supernatant; Add again 10 mL acetonitriles to centrifuge tube, repeat aforesaid operations 1 time, merge extracted twice liquid;
Purify: in extract, add 60 mg N-propyl group ethylenediamine and anhydrous magnesium sulfates, vortex mixed 1 min, 20 ℃ of lower centrifugal 10 min of 4000 r/min, get supernatant, add the dissolving of 0.5 mL methyl alcohol in 40 ℃ of lower Rotary Evaporators evaporates to dryness, residue used, centrifugal, get supernatant, to be analyzed;
(2) adopt liquid chromatography-mass spectrography to measure
Chromatographic condition: Agilent ZORBAX SB-C
18, 4.6 mm * 250 mm, 5 μ m; Mobile phase A: contain 20% methanol-water solution of 5 mmol/L ammonium formates, Mobile phase B: contain the methanol solution of 5 mmol/L ammonium formates, elution program: 0-5 min, 26%B ~ 52%B, 5 ~ 15 min, 52% B ~ 70%B, 15 ~ 45 min, 70% B ~ 83%B, 45 ~ 46 min, 83% B ~ 100%B, 46 ~ 65 min, 100% B, analysis times 65 min, equilibration time 20 min, flow velocity: 0.5 mL/min, column temperature: 20 ℃, sample size: 20 μ L;
Mass spectrum condition: electro-spray ionization, positive ion SIM mode detection, fragment voltage 100 V, atomization gas pressure 40 psi, dry gas flow velocity 11 L/min, 350 ° of C of dry gas temperature, capillary voltage 3500 V;
Described agricultural chemicals is respectively: acephatemet, pymetrozine, Diacloden, Imidacloprid, pyridine worm miaow, carbendazim, thiophanate methyl, triforine, methidathion, Fluoxastrobin, cough up bacterium piperazine, triazolone, procymidone, napropamide, Tolylfluanid, Tebuconazole, diazinon, phonetic bacterium sulfanilamide (SN), zolone, pirimiphos-methyl, Difenoconazole, pyrethrins, fluorine bacterium azoles; Corresponding m/z value is: 142,192,218,223,226,256,266,272,292,294,301,303,305,306,308,343,346,364,373,385,390,404 and 406.
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| CN103210926A (en) * | 2013-04-26 | 2013-07-24 | 华中农业大学 | Bactericide for preventing and treating sclerotinia rot of colza and preparation method thereof |
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| CN105259267B (en) * | 2015-10-28 | 2018-01-16 | 江门市植保有限公司 | A kind of method for determining Fluoxastrobin and/or Tebuconazole content |
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| CN108872439A (en) * | 2018-08-07 | 2018-11-23 | 中国农业科学院茶叶研究所 | The extraction and purification methods of pymetrozine residual quantity in a kind of measurement tealeaves |
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