CN107045023B - Method that is a kind of while measuring Common Herbicides residual quantity in tobacco - Google Patents
Method that is a kind of while measuring Common Herbicides residual quantity in tobacco Download PDFInfo
- Publication number
- CN107045023B CN107045023B CN201710157643.0A CN201710157643A CN107045023B CN 107045023 B CN107045023 B CN 107045023B CN 201710157643 A CN201710157643 A CN 201710157643A CN 107045023 B CN107045023 B CN 107045023B
- Authority
- CN
- China
- Prior art keywords
- tobacco
- solution
- acetone
- standard
- sample
- 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.)
- Expired - Fee Related
Links
Classifications
-
- 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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- 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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/14—Preparation by elimination of some components
-
- 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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
-
- 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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/067—Preparation by reaction, e.g. derivatising the sample
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a kind of methods for measuring Common Herbicides residual quantity in tobacco simultaneously, this method are as follows: the acidified acetonitrile of object extracts in tobacco sample, it is purified with florisil silica solid phase extraction column, acetone/hexamethylene mixed liquor of volume ratio position 3:7 elutes, trimethyl silicone hydride diazomethane derivatization is used after eluent concentration, online gel permeation chromatography-gas chromatography tandem mass spectrometry combined instrument is recycled to be detected.Compared with standard method, the Testing index of four standard methods is incorporated, and chlorthal is added, the present invention significantly improves detection working efficiency simultaneously, sensitivity with higher, anti-interference ability, ensure that the full extent sample high-recovery and optimal reproducibility.
Description
Technical field
The invention belongs to Pesticide Residues in Tobacco detection field, it is related to pesticide residue determination technology in tobacco, more particularly to
The measuring method of Common Herbicides residual quantity in tobacco, specifically detection tobacco in dicamba, 2,4- drop, trefanocide, benfluralin,
2,4,5- tears, clomazone, diphenamide, alachlor, napropamide, chlorthal, butralin, isopropalin, pendimethalin, fluorine
Save the residual quantity of amine, nitrofen and efficient fluazifop totally 16 kinds of herbicides.
Background technique
Tobacco is the important industrial crops in China, and in recent years, the application of herbicide significantly reduces labor intensity, has
Effect improves agricultural production efficiency, plays positive effect to yield of tobacco and quality.With the expansion of herbicide use scope,
It remains to endanger caused by human health and environment and have been to be concerned by more and more people, the residual especially in water environment,
It can be migrated in farmland ecosystem, soil, underground water, atmosphere etc. is caused to pollute.Some researches show that the herbicides such as phenoxy carboxylic acid
It can cause human soft tissue malignant tumour, placenta toxicity is also shown to animal body.
International tobacco scientific research Cooperation Centre (CORESTA) agricultural chemicals Advisory Board (ACAC) was in 2013
The guiding residue limits (Guidance Residue Levels, GRLs) of 120 kinds of pesticides in tobacco are proposed, wherein providing
Belong to the guiding residue limits of 6 15 kinds of herbicides of big classification.It is respectively: 1) 3 kinds of phenoxy carboxylic acid (0.2 mg/ of dicamba
0.2 mg/kg and 2,4,5- tears of kg, 2,4- drop, 0.05 mg/kg)；2) 2 kinds of amides (0.05 mg/kg of diphenamide and first
Careless 0.1 mg/kg of amine)；3) 6 kinds of dinitroaniline (5 mg/kg of butralin, 0.07 mg/kg of isopropalin, pendimethalin 5
Mg/kg, 0.1 mg/kg of 0.06 mg/kg of flumetralim, 0.06 mg/kg of benfluralin and trefanocide)；4) a kind of (weeding of diphenyl ether
0.02 mg/kg of ether)；5) a kind of aryloxyphenoxypropanoates class (1.0 mg/kg of efficient fluazifop)；6) 2 kinds of organic heterocyclic class it is (different
0.5 mg/kg of 0.2 mg/kg of oxadiazon and chlorthal).
Currently, 4 professional standards: 1) " YC/T 181-2004 tobacco need to be used by completing the detection of above-mentioned 15 kinds of herbicides
And the measurement gas chromatography of the organic chloroacetamide herbicide persticide residue of tobacco product, detectable dicamba, 2,4- drop and 2,4,
5- tears；2) " the measurement gas chromatography of YC/T 179-2004 tobacco and tobacco product acetamide-group herbicides persticide residue,
Detectable alachlor, diphenamide and napropamide "；3) " YC/T 405.3-2011 tobacco and tobacco product Multiple Pesticides are residual
The measurement third portion of allowance: gas chromatography combined with mass spectrometry and gas chromatography can detect alachlor, benfluralin, butralin, fluorine
Save amine, isopropalin, nitrofen, trefanocide "；4) " YC/T 405.1-2011 tobacco and tobacco product Multi-pesticide residues
Measurement part 1: high performance liquid chromatography-tandem mass method can detect clomazone, diphenamide, smart pyrrole fluorine dogstail
Spirit "." Chen Xiaoshui, Bian Zhaoyang, Tang Gangling wait 132 kinds of agricultures in gas chromatography tandem mass spectrometry technology analysis tobacco to document
Medicine remains [J] chromatography, 2012,30 (10): 1043-1055. " can be only done wherein 10 kinds of herbicide residue detections, and (fluorine is happy
Spirit, benfluralin, clomazone, alachlor, chlorthal, isopropalin, pendimethalin, flumetralim, diphenamide, nitrofen).
Existing examination criteria and document cannot a method measure 15 kinds of herbicide residues of above-mentioned regulation limitation in tobacco simultaneously, deposit
The problem of detection efficiency is low, cumbersome and time-consuming, therefore, 15 kinds for establishing while measuring above-mentioned regulation limitation in tobacco
The method of herbicide residue is extremely urgent.
16 kinds of herbicides that the present invention refers to increase chlorthal wherein 15 kinds are respectively in above-mentioned 4 tobacco business standards
Testing index, more fully covering currently herbicide residue amount Testing index in tobacco is required both at home and abroad.
Summary of the invention
The technical problem to be solved by the present invention is providing side that is a kind of while measuring Common Herbicides residual quantity in tobacco
Method, this method can measure dicamba in tobacco, 2,4- drop, trefanocide, benfluralin, 2,4,5- tears, clomazone, double benzoyls simultaneously
Careless amine, alachlor, napropamide, chlorthal, butralin, isopropalin, pendimethalin, flumetralim, nitrofen and smart pyrrole fluorine dogstail
The residual quantity of spirit, more fully covering currently both at home and abroad requires herbicide residue amount Testing index in tobacco, existing to solve
The problem of technology.
The technical scheme adopted by the invention is as follows: a method of Common Herbicides residual quantity in tobacco being measured simultaneously, it is special
Sign is: the acidified acetonitrile of object extracts in tobacco sample, is purified with florisil silica solid phase extraction column, acetone/hexamethylene
The mixed liquor of alkane (volume ratio 3:7) elutes, and uses trimethyl silicone hydride diazomethane derivatization after eluent concentration, recycles online
Gel permeation chromatography-gas chromatography tandem mass spectrometry combined instrument is detected.
Method that is a kind of while measuring Common Herbicides residual quantity in tobacco, the specific operating procedure of this method are as follows::
(1) preparation of inner mark solution: the acetone inner mark solution that pretilachlor concentration is 10 μ g/mL is prepared；
(2) derivating agent: 2 mol/L trimethyl silicone hydride diazomethane hexane solutions；
(3) extraction of herbicidal target: weighing the tobacco sample of 2.00 g drying milled, and 2 mL ultrapure waters profit is added
It is molten to sequentially add 2 g sodium chloride, the second eyeball of inner mark solution, 10 mL containing 1 % acetic acid of 50 μ L steps (1) preparation by wet 10 min
Liquid is vortexed with 2500 rpm and shakes 5 min, then is centrifuged 5 min with 5000 r/min, to be clean；
(4) florisil silica solid-phase extraction column activates: activating pillar with 5 mL acetone/hexamethylene mixed liquor, discards outflow
Liquid；
(5) florisil silica Solid Phase Extraction column purification: extracting solution to step (4) for accurately pipetting 2 mL steps (3) activate
In solid-phase extraction column afterwards, pillar, acetone/cyclohexane volume ratio 3:7 are eluted with 10 mL acetone/hexamethylene mixed liquor, collection is washed
De- liquid is into tool cover glass test tube；
(6) eluent is concentrated: the eluent that step (5) obtains being blown in 40 DEG C of water-bath nitrogen and is concentrated into 1mL, wait derive
Change；
(7) derivatization: being added the derivating agent of 100 μ L steps (2) in step (6) concentrate, and tool lid sealing is vortexed mixed
It is even, it is placed in 40 DEG C of water-baths and performs the derivatization 30 min of reaction, 40 DEG C of nitrogen, which are blown, is concentrated into close dry, accurate addition volume ratio 3:
7 be 1 mL acetone/hexamethylene, is vortexed and mixes, cross 0.45 μm of organic phase filter membrane, detects to GPC-GC-MS/MS；
(8) standard reserving solution is prepared: weighing dicamba, 2,4- drop, trefanocide, the benfluralin, 2,4,5- of 10 mg respectively
Tears, clomazone, diphenamide, alachlor, napropamide, chlorthal, butralin, isopropalin, pendimethalin, flumetralim,
The standard inventory of 1000 μ g/mL is made with acetone constant volume in 10 mL volumetric flasks in nitrofen and efficient fluazifop standard items
Liquid, -20 DEG C of preservations；
(9) mixed standard solution preparation: take each 100 μ L of step (8) Plays stock solution into 10 mL volumetric flasks, with third
Ketone is diluted to scale, and the mixed standard solution of 10 μ g/mL, 2 ~ 8 DEG C of preservations are made；
(10) configuration of blank tobacco sample matrix working solution: the mixed standard solution of step (9) is taken, with different bodies
Product is added in the extraction matrix of step (6) to the blank tobacco leaf of derivatization, performs the derivatization by step (7), and various concentration is made
16 kinds of herbicide tobacco matrix standard working solutions, be vortexed mix, cross 0.45 μm of organic phase filter membrane, to GPC-GC-MS/MS examine
It surveys；
(11) GPC-GC-MS/MS is measured: by the matrix hybrid standard in step (7) in sample extracting solution and step (10)
Solution, injection GPC-GC-MS/MS are measured；
(12) result calculates: carrying out regression analysis to its respective concentration with relative peak area by internal standard method, calculates sample
The content of 16 kinds of herbicides in prepare liquid.
Preferably, the condition of use when GPC is measured in above-mentioned steps (11) are as follows: chromatographic column is Shodex CLNpak
EV-200 (2.1 mm x, 150 mm), mobile phase are acetone-hexamethylene mixed solution, and acetone and cyclohexane volume ratio are 3:7,
Flow velocity is 0.1 mL/min, and column temperature is 40 DEG C, and sample volume is 10 μ L, and the Hoarding segment of object is 3.46 ~ 3.57 min.
Preferably, the condition used when GC-MS/MS is measured in above-mentioned steps (11) are as follows: chromatographic column is inertia quartz capillary
Pipe: pre-column (5 m x, 0.53 mm), trapping column are DB-5 MS column (0.25 μm of 5 m x, 0.25 mm x), splitter DB-
5MS column (0.25 μm of 25 m x, 0.25 mm x)；PTV sample introduction mode；Injection port temperature program: 120 DEG C (keeping 5 min),
250 DEG C (keeping 30 min) are risen to 100 DEG C/min；Chromatographic column temperature program: 82 DEG C (keeping 5 min), with 8 DEG C/min
280 DEG C (keeping 5 min) are risen to, total run time is 30 min；Electron impact ion source (EI)；Electron energy: 70 eV；From
Source temperature: 230 DEG C；Interface temperature: 280 DEG C；The solvent delay time: 12 min；Detector voltage: 1.0 KV；Collision gas
Flow velocity: 1.5 mL/min of helium；Data scanning mode: cation；Mensuration mode: Selective reaction monitoring mode (MRM).
Preferably, GPC-GC/MSMS measures concrete operations in above-mentioned steps (11) are as follows: takes tobacco extract and various concentration
Dicamba, 2,4- drop, trefanocide, benfluralin, 2,4,5- tears, clomazone, diphenamide, alachlor, napropamide, enemy grass
Rope, butralin, isopropalin, pendimethalin, flumetralim, nitrofen and efficient fluazifop blank tobacco matrix hybrid standard
Solution, injection GPC-GC-MS/MS are measured, and carry out regression analysis, meter to its respective concentration with relative peak area by internal standard method
Calculate dicamba in sample prepare liquid, 2,4- drop, trefanocide, benfluralin, 2,4,5- tears, clomazone, diphenamide, first grass
The content of amine, napropamide, chlorthal, butralin, isopropalin, pendimethalin, flumetralim, nitrofen and efficient fluazifop.
Beneficial effects of the present invention: compared with prior art, effect of the present invention is as follows:
(1) present invention can be measured the Testing index of 4 standard methods, and joined chlorthal, make detection kind
Reach 16 kinds, meet most of herbicide requirement in tobacco, reduce the process and preparation of every kind of herbicide of independent detection,
Greatly reduce testing cost；
(2) present invention can promote object to separate with matrix, be improved particularly using 1% acetic acid acetonitrile as Extraction solvent
The stability of phenoxy carboxylic acid herbicides, increases the rate of recovery；
(3) it is dry to remove alcohols and pigment of electronegativity etc. through florisil silica Solid Phase Extraction column purification for extracting solution of the present invention
Disturbing matter, such as sterol substance；It is further purified in conjunction with online gel permeation chromatography, eliminates the lipid and color of macromolecular
Element obtains cleaner upper machine solution, and the sharp symmetry of the peak shape of various objects is good, and mitigates to chromatographic column and ion source
Pollution；By Fig. 4, Fig. 5 SCAN spectrogram NIST05 library searching result it is found that main interference impurity be alcohols material；
(4) present invention selects mobile phase acetone/hexamethylene (volume ratio 3:7) mixed liquor conduct of online gel permeation chromatography
The eluent of solid-phase extraction column, only 10 mL eluents can elute whole objects, and the volatile volume of eluent is few, makes
It is more easy to obtain pre-treatment operation；
(5) it is derivating agent that the present invention, which selects trimethyl silicone hydride diazomethane, to the dicamba of phenoxy carboxylic acid herbicides,
2,4- drops and 2,4,5- tears perform the derivatization, at the same the addition of derivating agent and have not been changed other type herbicides chemical property and
Structure, measurement while realizing 16 kinds of variety classes herbicides.
(6) present invention selects pretilachlor to make internal standard, accurately quantifies to 16 kinds of herbicides, improves the accurate of method
Property, caused error in matrix interference and pretreatment process is also effectively reduced；
(7) present invention combines the GC-MS analytical technology and means of online GPC purification, and online GPC is rich in fat, color
There is apparent advantage, the second order ms (MS/ of extension in terms of the sample isolation of purified of the macromoleculars such as element, alkaloid, polymer
MS) versus primary mass spectrum (MS), anti-interference ability is stronger, and the remains of pesticide suitable for the complex matrices sample such as tobacco quickly sieves
It looks into and confirms；
(8) compared with the past, the detection working time shorten to original a quarter, and testing cost is reduced to original three points
One of, detection working efficiency greatly improves.Method of the invention has the advantages that easy, quick, sensitive, accurate.
Detailed description of the invention
Fig. 1 is 16 kinds of herbicide standard items MRM spectrograms；
Fig. 2 is that tobacco blank sample adds 16 kinds of herbicide standard items MRM spectrograms；
Fig. 3 is tobacco blank sample MRM spectrogram；
Fig. 4 is tobacco extract SCAN spectrogram；
Fig. 5 is tobacco extract florisil silica Solid Phase Extraction column purification SCAN spectrogram.
Specific embodiment
With reference to the accompanying drawing and the present invention is described further in specific embodiment.
Embodiment 1: a method of measuring Common Herbicides residual quantity in tobacco simultaneously, it is characterised in that: tobacco sample
The middle acidified acetonitrile of object extracts, and is purified with florisil silica solid phase extraction column, acetone/hexamethylene (volume ratio 3:7)
Mixed liquor elution uses trimethyl silicone hydride diazomethane derivatization after eluent concentration, recycles online gel permeation chromatography-gas
Phase chromatography-tandem mass spectrum combined instrument is detected.
Method that is a kind of while measuring Common Herbicides residual quantity in tobacco, the specific operating procedure of this method are as follows::
(1) preparation of inner mark solution: the acetone inner mark solution that pretilachlor concentration is 10 μ g/mL is prepared；
(2) derivating agent: 2 mol/L trimethyl silicone hydride diazomethane hexane solutions；
(3) extraction of herbicidal target: weighing the tobacco sample of 2.00 g drying milled, and 2 mL ultrapure waters profit is added
It is molten to sequentially add 2 g sodium chloride, the second eyeball of inner mark solution, 10 mL containing 1 % acetic acid of 50 μ L steps (1) preparation by wet 10 min
Liquid is vortexed with 2500 rpm and shakes 5 min, then is centrifuged 5 min with 5000 r/min, to be clean；
(4) florisil silica solid-phase extraction column activates: activating pillar with 5 mL acetone/hexamethylene mixed liquor, discards outflow
Liquid；
(5) florisil silica Solid Phase Extraction column purification: extracting solution to step (4) for accurately pipetting 2 mL steps (3) activate
In solid-phase extraction column afterwards, pillar, acetone/cyclohexane volume ratio 3:7 are eluted with 10 mL acetone/hexamethylene mixed liquor, collection is washed
De- liquid is into tool cover glass test tube；
(6) eluent is concentrated: the eluent that step (5) obtains being blown in 40 DEG C of water-bath nitrogen and is concentrated into 1mL, wait derive
Change；
(7) derivatization: being added the derivating agent of 100 μ L steps (2) in step (6) concentrate, and tool lid sealing is vortexed mixed
It is even, it is placed in 40 DEG C of water-baths and performs the derivatization 30 min of reaction, 40 DEG C of nitrogen, which are blown, is concentrated into close dry, accurate addition volume ratio 3:
7 be 1 mL acetone/hexamethylene, is vortexed and mixes, cross 0.45 μm of organic phase filter membrane, detects to GPC-GC-MS/MS；
(8) standard reserving solution is prepared: weighing dicamba, 2,4- drop, trefanocide, the benfluralin, 2,4,5- of 10 mg respectively
Tears, clomazone, diphenamide, alachlor, napropamide, chlorthal, butralin, isopropalin, pendimethalin, flumetralim,
The standard inventory of 1000 μ g/mL is made with acetone constant volume in 10 mL volumetric flasks in nitrofen and efficient fluazifop standard items
Liquid, -20 DEG C of preservations；
(9) mixed standard solution preparation: take each 100 μ L of step (8) Plays stock solution into 10 mL volumetric flasks, with third
Ketone is diluted to scale, and the mixed standard solution of 10 μ g/mL, 2 ~ 8 DEG C of preservations are made；
(10) configuration of blank tobacco sample matrix working solution: the mixed standard solution of step (9) is taken, with different bodies
Product is added in the extraction matrix of step (6) to the blank tobacco leaf of derivatization, performs the derivatization by step (7), and various concentration is made
16 kinds of herbicide tobacco matrix standard working solutions, be vortexed mix, cross 0.45 μm of organic phase filter membrane, to GPC-GC-MS/MS examine
It surveys；
(11) GPC-GC-MS/MS is measured: by the matrix hybrid standard in step (7) in sample extracting solution and step (10)
Solution, injection GPC-GC-MS/MS are measured；
(12) result calculates: carrying out regression analysis to its respective concentration with relative peak area by internal standard method, calculates sample
The content of 16 kinds of herbicides in prepare liquid.
Preferably, the condition of use when GPC is measured in above-mentioned steps (11) are as follows: chromatographic column is Shodex CLNpak
EV-200 (2.1 mm x, 150 mm), mobile phase are acetone-hexamethylene mixed solution, and acetone and cyclohexane volume ratio are 3:7,
Flow velocity is 0.1 mL/min, and column temperature is 40 DEG C, and sample volume is 10 μ L, and the Hoarding segment of object is 3.46 ~ 3.57 min.
Preferably, the condition used when GC-MS/MS is measured in above-mentioned steps (11) are as follows: chromatographic column is inertia quartz capillary
Pipe: pre-column (5 m x, 0.53 mm), trapping column are DB-5 MS column (0.25 μm of 5 m x, 0.25 mm x), splitter DB-
5MS column (0.25 μm of 25 m x, 0.25 mm x)；PTV sample introduction mode；Injection port temperature program: 120 DEG C (keeping 5 min),
250 DEG C (keeping 30 min) are risen to 100 DEG C/min；Chromatographic column temperature program: 82 DEG C (keeping 5 min), with 8 DEG C/min
280 DEG C (keeping 5 min) are risen to, total run time is 30 min；Electron impact ion source (EI)；Electron energy: 70 eV；From
Source temperature: 230 DEG C；Interface temperature: 280 DEG C；The solvent delay time: 12 min；Detector voltage: 1.0 KV；Collision gas
Flow velocity: 1.5 mL/min of helium；Data scanning mode: cation；Mensuration mode: Selective reaction monitoring mode (MRM).
Preferably, GPC-GC/MSMS measures concrete operations in above-mentioned steps (11) are as follows: takes tobacco extract and various concentration
Dicamba, 2,4- drop, trefanocide, benfluralin, 2,4,5- tears, clomazone, diphenamide, alachlor, napropamide, enemy grass
Rope, butralin, isopropalin, pendimethalin, flumetralim, nitrofen and efficient fluazifop blank tobacco matrix hybrid standard
Solution, injection GPC-GC-MS/MS are measured, and carry out regression analysis, meter to its respective concentration with relative peak area by internal standard method
Calculate dicamba in sample prepare liquid, 2,4- drop, trefanocide, benfluralin, 2,4,5- tears, clomazone, diphenamide, first grass
The content of amine, napropamide, chlorthal, butralin, isopropalin, pendimethalin, flumetralim, nitrofen and efficient fluazifop.
Embodiment 2: the detection of 16 kinds of herbicide residue amounts in tobacco sample
1. instrument and reagent:
Online gel permeation chromatography-gas chromatography tandem mass spectrometry combined system (Online GPCGCMS/MS system) (day
This Shimadzu Corporation), including SIL20ADvp autosampler, ShodexEV200A gel permeation chromatographic column, CEO20ASvp column temperature
Case, SPD20Avp UV detector, QP2010Plus gas chromatograph, TQ8040 type mass spectrometer, PTV2010 large volume into
Sample device, X-22R high speed freezing centrifuge (Allegra company, the U.S.), vortex oscillator (TAIBOYS company, the U.S.), AL204 points
It analyses balance (Mettler company, the U.S.), TurboVap II nitrogen evaporator (Biotage company, Sweden).
Acetonitrile (chromatographically pure), acetone (chromatographically pure), hexamethylene (chromatographically pure), sodium chloride (the residual grade of agriculture), acetic acid (chromatographically pure)；
Experimental water is Milipore-Q ultrapure water；Derivating agent: 2 mol/L trimethyl silicone hydride diazomethane hexane solutions (north
Capital lark prestige).
Standard items: dicamba, 2,4- drop, trefanocide, benfluralin, 2,4,5- tears, clomazone, diphenamide, first grass
Amine, napropamide, chlorthal, butralin, isopropalin, pendimethalin, flumetralim, nitrofen, efficient fluazifop and pretilachlor
(internal standard), (purity is greater than 98.0%, German DR company).
Standard reserving solution is prepared: weigh respectively the dicamba of 10 mg, 2,4- drop, trefanocide, benfluralin, 2,4,5- tears,
Clomazone, diphenamide, alachlor, napropamide, chlorthal, butralin, isopropalin, pendimethalin, flumetralim, weeding
The standard inventory of 1000 μ g/mL is made with acetone constant volume in 10 mL volumetric flasks in the standard items of ether and efficient fluazifop
Liquid, -20 DEG C of preservations；
Mixed standard solution preparation: it takes each 100 μ L of above-mentioned standard stock solution into 10 mL volumetric flasks, is diluted to acetone
16 kinds of herbicide mixed standard solutions of 10 μ g/mL, 2 ~ 8 DEG C of preservations are made in scale
The preparation of inner mark solution: the acetone inner mark solution that preparation pretilachlor concentration is 10 μ g/mL according to the above method, 2 ~ 8
DEG C save；
2. sample treatment:
(1) extraction of herbicidal target: weighing the tobacco sample of 2.00 g drying milled, and 2 mL ultrapure waters profit is added
Wet 10 min sequentially adds the second eyeball solution that 2 g sodium chloride, 50 μ L inner mark solutions, 10 mL contain 1 % acetic acid, with 2500 rpm
Be vortexed 5 min of concussion, then is centrifuged 5 min with 5000 r/min, and extracting solution is to be clean；
(2) florisil silica solid phase extraction column activates: living with 5 mL acetone/hexamethylene (volume ratio 3:7) mixed solution
Change pillar, discards efflux；
(3) florisil silica solid phase extraction column purifies: accurately pipetting solid-phase extraction column of the 2 mL extracting solutions to after activating
In, pillar is eluted with 10 mL acetone/hexamethylene (volume ratio 3:7) mixed liquor, collects eluent into tool cover glass test tube；
4) eluent is concentrated: about 1 mL will be concentrated into the nitrogen evaporator of eluent water-bath at 40 DEG C；
(5) derivatization: being added 100 μ L derivating agents in concentrate, and tool lid sealing, which is vortexed, to be mixed, and is placed in 40 DEG C of water-baths
Middle progress 30 min of derivatization reaction blows in 40 DEG C of nitrogen and is concentrated into close dry, addition 1mL acetone/hexamethylene (volume ratio 3:7) mixing
Liquid is vortexed and mixes, and crosses 0.45 μm of organic phase filter membrane, detects to GPC-GC-MS/MS；
Mass Spectrometry Conditions (GPC-GC-MS/MS) measurement 3. online gel permeation chromatography-gas-chromatography one is connected:
(1) online GPC condition: chromatographic column is Shodex CLNpak EV-200 (2.1 mm x, 150 mm)；Mobile phase
For acetone-hexamethylene (volume ratio 3:7) mixed solution；Flow velocity is 0.1 mL/min；Column temperature is 40 DEG C；Carrier gas purge
0.1min；Sample volume is 10 μ L；The Hoarding segment of object is 3.46 ~ 3.57 min.
(2) GC-MS/MS condition: chromatographic column is inertia quartz capillary: pre-column (5 m x, 0.53 mm), trapping column are
DB-5 MS column (0.25 μm of 5 m x, 0.25 mm x), splitter are DB-5MS column (25 m x, 0.25 mm x, 0.25 μ
m)；PTV sample introduction mode；Injection port temperature program: 120 DEG C (keeping 5 min), 250 DEG C is risen to 100 DEG C/min and (keeps 30
Min)；Chromatographic column temperature program: 70 DEG C (keeping 5 min), 280 DEG C (keeping 5 min) are risen to 8 DEG C/min, always when operation
Between be 30 min；Electron impact ion source (EI)；Electron energy: 70 eV；Ion source temperature: 230 DEG C；Interface temperature: 280
℃；The solvent delay time: 12 min；Detector voltage: 1.0 KV；Collision gas flow velocity: 1.5 mL/min of helium；Data scanning side
Formula: cation；Mensuration mode: Selective reaction monitoring mode (MRM), main mass spectrometry parameters are shown in Table 1.
1 16 kinds of herbicides of table and interior target retention time and mass spectrometry parameters
| Sequence Number | Chinese is logical With name | English name | Retention time (min) | Quota ion pair (m/z) | Impact energy It measures (v) | Qualitative ion pair (m/z) | Collision energy (v) |
| 1 | Dicamba | Dicamba | 12.24 | 203>188 | 15 | 203>175 | 14 |
| 2 | 2,4- drop | 2,4-D | 14.48 | 199>156 | 12 | 199>125 | 15 |
| 3 | Trefanocide | Trifluralin | 15.16 | 306>264 | 15 | 264>160 | 10 |
| 4 | Benfluralin | Benfluralin | 15.35 | 292> 264 | 10 | 292>160 | 21 |
| 5 | 2,4,5- Tears | 2,4,5-T | 17.48 | 233>190 | 25 | 233>159 | 18 |
| 6 | Different evil grass Ketone | Clomazone | 18.85 | 204>107 | 18 | 125> 89 | 15 |
| 7 | Alachlor | Alachlor | 19.17 | 188>160 | 10 | 160>132 | 10 |
| 8 | Chlorthal | Chlorthal- dimethyl | 19.65 | 331> 301 | 10 | 301>223 | 20 |
| 9 | Butralin | Butralin | 21.46 | 266>220 | 10 | 266>190 | 15 |
| 10 | Isopropyl is happy Spirit | Isopropalin | 22.22 | 280>238 | 10 | 280>180 | 15 |
| 11 | Diformazan penta Spirit | Pendimethali n | 22.49 | 252>162 | 12 | 252>191 | 8 |
| 12 | Flumetralim | Flumetralin | 23.10 | 143> 107 | 20 | 143>108 | 20 |
| 13 | Double benzoyls Careless amine | Diphenamid | 24.23 | 239>167 | 8 | 167>165 | 15 |
| 14 | Napropamide | Napropamid | 25.46 | 271>128 | 10 | 128>72 | 20 |
| 15 | Nitrofen | Nitrofen | 28.13 | 283>162 | 25 | 283>202 | 15 |
| 16 | Smart pyrrole fluorine Diclofop-methyl | Fluazifop- butyl | 28.38 | 282>91 | 15 | 383>282 | 10 |
| IS | Pretilachlor | Pretilachlor | 20.78 | 238>176 | 20 | 162>132 | 25 |
4. matrix matching standard curve and minimum detectability
(1) 5 parts of blank tobacco samples are weighed, are handled by step " 2. sample treatments: (1) ~ (4) ", 1 mL is prepared
Blank tobacco sample matrix extracting solution, in 10 mL teat glass, for use；
(2) mixed standard solution of 16 kinds of herbicides of 5,10,20,40,80 μ L is pipetted, until being equipped with blank tobacco sample
In the teat glass of matrix extracting solution, it being separately added into 100 μ L derivating agents, tool lid seals 40 DEG C of water-bath derivatization 30 min, and 40
DEG C nitrogen blows close dry, and 1 mL acetone/hexamethylene (volume ratio 3:7) mixed solution is added, mixes, is made into the matrix with concentration gradient
Hybrid standard working solution.The concentration of the series standard solution of preparation is respectively as follows: 0.05,0.1,0.2,0.4,0.8 μ g/mL；
(3) after matrix hybrid standard working solution crosses 0.45 μm of organic filter membrane, injection GPC-GC-MS/MS is measured.
And ratio (Y) and the progress linear regression analysis of its concentration (X) to each standard specimen peak area and interior target peak area, obtain standard song
Line.The result shows that with the peak area that measures in good linear relationship, related coefficient within the scope of 0.05~0.8 μ g/mL
(γ) is all larger than 0.99.It is respectively 0.002~0.02 according to the detection limit (LOD) that 3 times of signal-to-noise ratio (S/N) calculate 16 kinds of herbicides
Mg/kg, see Table 2 for details.
The detection limit of the linear equations of 2 16 kinds of herbicides of table, related coefficient sum
| Serial number | Herbicide | Linear equation | Related coefficient (γ) | Detection limit (mg/kg) |
| 1 | Dicamba | y=4.4632*x-0.3451 | 0.9995 | 0.004 |
| 2 | 2,4- drop | y=7.2341*x-0.0023 | 0.9976 | 0.008 |
| 3 | Trefanocide | y=3.8460*x-0.3022 | 0.9967 | 0.002 |
| 4 | Benfluralin | y=2.7681*x-0.0092 | 0.9995 | 0.009 |
| 5 | 2,4,5- tears | y=4.3233*x-0.0752 | 0.9979 | 0.008 |
| 6 | Clomazone | y=7.8975*x-0.0294 | 0.9998 | 0.008 |
| 7 | Alachlor | y=12.3039*x-0.1990 | 0.9954 | 0.006 |
| 8 | Chlorthal | y=0.9635*x-0.0779 | 0.9997 | 0.005 |
| 9 | Butralin | y=1.8997*x-0.0678 | 0.9923 | 0.004 |
| 10 | Isopropalin | y=6.0398*x-0.0127 | 0.9999 | 0.008 |
| 11 | Pendimethalin | y=8.7066*x-0.0103 | 0.9945 | 0.01 |
| 12 | Flumetralim | y=6.0004*x-0.0201 | 0.9997 | 0.006 |
| 13 | Diphenamide | y=1.0709*x-0.0728 | 0.9945 | 0.006 |
| 14 | Napropamide | y=7.0298*x-0.1671 | 0.9967 | 0.004 |
| 15 | Nitrofen | y=4.3109*x-0.0445 | 0.9995 | 0.02 |
| 16 | Efficient fluazifop | y=9.0334*x-0.0034 | 0.9979 | 0.01 |
5. the rate of recovery and repeatability of the method for the present invention:
Blank sample is chosen, accurately adds the 16 of basic, normal, high three concentration levels (0.05,0.1,0.2 mg/kg) respectively
Kind herbicide mixed standard solution, and pre-treatment and GPC-GC-MS/MS analysis are carried out by preceding method, with scalar quantity and measurement
The rate of recovery of the ratio calculation method of value, with the repeatability of 6 result computational methods of each horizontal replication.As a result table
Bright, the average recovery rate of 16 kinds of herbicides is the % of 85.4 %~107.9, and relative standard deviation (RSD) is the % of 2.8 % ~ 13.2.Knot
Fruit meets international tobacco scientific research Cooperation Centre (CORESTA) agricultural chemicals Advisory Board (ACAC) and instructs residue limits
(GRLs) and technical method instructs the requirement to the rate of recovery, precision, the results are shown in Table 3.
The rate of recovery and repeatability (n=6) of 3 16 kinds of herbicides of table
| Herbicide | Blank sample (mg/kg) | The rate of recovery (mg/kg) | RSD(%) | The rate of recovery (mg/kg) | RSD(%) | The rate of recovery (mg/kg) | RSD(%) |
| Dicamba | 0.00 | 85.4 | 6.5 | 89.9 | 5.4 | 94.6 | 4.5 |
| 2,4- drop | 0.00 | 87.5 | 8.9 | 86.3 | 6.3 | 86.3 | 6.7 |
| Trefanocide | 0.00 | 97.3 | 9.6 | 96.7 | 7.4 | 91.0 | 8.6 |
| Benfluralin | 0.00 | 78.9 | 10.6 | 88.9 | 5.8 | 92.3 | 6.7 |
| 2,4,5- tears | 0.00 | 87.2 | 9.5 | 91.4 | 12.3 | 105.6 | 9.7 |
| Clomazone | 0.00 | 96.7 | 5.7 | 98.0 | 6.7 | 97.8 | 4.9 |
| Alachlor | 0.00 | 95.3 | 9.3 | 86.5 | 7.9 | 85.8 | 4.8 |
| Chlorthal | 0.00 | 107.9 | 4.6 | 103.3 | 7.3 | 95.3 | 6.3 |
| Butralin | 0.00 | 92.3 | 13.4 | 86.8 | 8.4 | 89.9 | 7.1 |
| Isopropalin | 0.00 | 89.1 | 14.9 | 89.1 | 88.4 | 101.4 | 5.9 |
| Pendimethalin | 0.00 | 95.7 | 7.9 | 94.3 | 9.4 | 95.7 | 7.3 |
| Flumetralim | 0.00 | 87.4 | 6.7 | 88.0 | 2.8 | 90.4 | 4.3 |
| Diphenamide | 0.00 | 93.4 | 6.1 | 89.3 | 6.7 | 98.4 | 4.6 |
| Napropamide | 0.00 | 89.5 | 9.0 | 90.6 | 5.8 | 95.9 | 7.3 |
| Nitrofen | 0.00 | 88.7 | 13.2 | 97.0 | 9.4 | 99.4 | 8.1 |
| Efficient fluazifop | 0.00 | 100.2 | 6.5 | 105.9 | 5.4 | 102.3 | 4.5 |
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain
Within protection scope of the present invention, therefore, protection scope of the present invention should be based on the protection scope of the described claims lid.
Claims (3)
1. a kind of method for measuring Common Herbicides residual quantity in tobacco simultaneously, it is characterised in that: object passes through in tobacco sample
Acidifying acetonitrile is extracted, and is purified with florisil silica solid phase extraction column, and volume ratio is that acetone/hexamethylene mixed liquor of 3:7 is washed
It is de-, trimethyl silicone hydride diazomethane derivatization is used after eluent concentration, recycles online gel permeation chromatography-gas-chromatography-
Tandem mass spectrum combined instrument is detected, and the specific operating procedure of this method is as follows::
(1) preparation of inner mark solution: the acetone inner mark solution that pretilachlor concentration is 10 μ g/mL is prepared；
(2) derivating agent: 2 mol/L trimethyl silicone hydride diazomethane hexane solutions；
(3) extraction of herbicidal target: weighing the tobacco sample of 2.00 g drying milled, and 2 mL ultrapure waters wetting 10 is added
Min sequentially adds the second eyeball solution that 2 g sodium chloride, the inner mark solution that 50 μ L steps (1) are prepared, 10 mL contain 1 % acetic acid, with
2500 rpm, which are vortexed, shakes 5 min, then is centrifuged 5 min with 5000 r/min, to be clean；
(4) florisil silica solid-phase extraction column activates: activating pillar with 5 mL acetone/hexamethylene mixed liquor, discards efflux；
(5) florisil silica Solid Phase Extraction column purification: after the extracting solution to step (4) activation for accurately pipetting 2 mL steps (3)
In solid-phase extraction column, pillar is eluted with 10 mL acetone/hexamethylene mixed liquor, acetone/cyclohexane volume ratio 3:7 collects eluent
Into tool cover glass test tube；
(6) eluent is concentrated: the eluent that step (5) obtains being blown in 40 DEG C of water-bath nitrogen and is concentrated into 1mL, to derivatization；
(7) derivatization: being added the derivating agent of 100 μ L steps (2) in step (6) concentrate, and sealing, which is vortexed, to be mixed, and is placed in
30 min of reaction are performed the derivatization in 40 DEG C of water-baths, 40 DEG C of nitrogen, which blow to be concentrated into, closely to be done, and accurate addition volume ratio is the 1 of 3:7
ML acetone/hexamethylene is vortexed and mixes, and crosses 0.45 μm of organic phase filter membrane, detects to GPC-GC-MS/MS；
(8) standard reserving solution is prepared: weighing the dicamba of 10 mg, 2,4- drop, trefanocide, benfluralin, 2,4,5- tears, different respectively
Oxadiazon, diphenamide, alachlor, napropamide, chlorthal, butralin, isopropalin, pendimethalin, flumetralim, nitrofen
With efficient fluazifop standard items, with acetone constant volume in 10 mL volumetric flasks, be made 1000 μ g/mL standard reserving solution, -20
DEG C save；
(9) mixed standard solution preparation: taking each 100 μ L of step (8) Plays stock solution into 10 mL volumetric flasks, dilute with acetone
It releases and is settled to 10 mL, the mixed standard solution of 10 μ g/mL, 2 ~ 8 DEG C of preservations are made；
(10) configuration of blank tobacco sample matrix working solution: the mixed standard solution of step (9) is taken, is added with different volumes
Enter in extraction matrix of the step (6) to the blank tobacco leaf of derivatization, performed the derivatization by step (7), the 16 of various concentration are made
Kind herbicide tobacco matrix standard working solution, is vortexed and mixes, and crosses 0.45 μm of organic phase filter membrane, detects to GPC-GC-MS/MS；
(11) GPC-GC-MS/MS is measured: the matrix hybrid standard in step (7) in sample extracting solution and step (10) is molten
Liquid, injection GPC-GC-MS/MS are measured；
(12) result calculates: carrying out regression analysis to its respective concentration with relative peak area by internal standard method, it is to be measured to calculate sample
The content of 16 kinds of herbicides in liquid；
The condition of use when GPC is measured in step (11) are as follows: chromatographic column is Shodex CLNpak EV-200, mobile phase third
Ketone-hexamethylene mixed solution, acetone and cyclohexane volume ratio are 3:7, and flow velocity is 0.1 mL/min, and column temperature is 40 DEG C, sample volume
For 10 μ L, the Hoarding segment of object is 3.46 ~ 3.57 min.
2. a kind of method for measuring Common Herbicides residual quantity in tobacco simultaneously according to claim 1, it is characterised in that:
The condition used when GC-MS/MS is measured in step (11) are as follows: chromatographic column is inertia quartz capillary: pre-column, trapping column DB-5
MS column, splitter are DB-5MS column；PTV sample introduction mode；Injection port temperature program: 120 DEG C, keep 5 min, with 100 DEG C/
Min rises to 250 DEG C, keeps 30 min；Chromatographic column temperature program:, keeping 5 min, rise to 280 DEG C with 8 DEG C/min by 82 DEG C,
5 min are kept, total run time is 30 min；Electron impact ion source EI；Electron energy: 70 eV；Ion source temperature: 230
℃；Interface temperature: 280 DEG C；The solvent delay time: 12 min；Detector voltage: 1.0 KV；Collision gas flow velocity: helium 1.5
mL/min；Data scanning mode: cation；Mensuration mode: Selective reaction monitoring mode MRM.
3. a kind of method for measuring Common Herbicides residual quantity in tobacco simultaneously according to claim 1, it is characterised in that:
GPC-GC/MSMS measures concrete operations in step (11) are as follows: takes dicamba, the 2,4- drop, fluorine of tobacco extract and various concentration
Happy spirit, benfluralin, 2,4,5- tears, clomazone, diphenamide, alachlor, napropamide, chlorthal, butralin, isopropyl are happy
Spirit, pendimethalin, flumetralim, nitrofen and efficient fluazifop blank tobacco matrix mixed standard solution, inject GPC-GC-
MS/MS is measured, and is carried out regression analysis to its respective concentration with relative peak area by internal standard method, is calculated in sample prepare liquid
Dicamba, 2,4- drop, trefanocide, benfluralin, 2,4,5- tears, clomazone, diphenamide, alachlor, napropamide, enemy's grass
The content of rope, butralin, isopropalin, pendimethalin, flumetralim, nitrofen and efficient fluazifop.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710157643.0A CN107045023B (en) | 2017-03-16 | 2017-03-16 | Method that is a kind of while measuring Common Herbicides residual quantity in tobacco |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710157643.0A CN107045023B (en) | 2017-03-16 | 2017-03-16 | Method that is a kind of while measuring Common Herbicides residual quantity in tobacco |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107045023A CN107045023A (en) | 2017-08-15 |
| CN107045023B true CN107045023B (en) | 2019-04-02 |
Family
ID=59545467
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710157643.0A Expired - Fee Related CN107045023B (en) | 2017-03-16 | 2017-03-16 | Method that is a kind of while measuring Common Herbicides residual quantity in tobacco |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107045023B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107607638B (en) * | 2017-08-22 | 2020-06-12 | 杭州谱景柏泰科技有限公司 | Method and kit for detecting aromatic compound |
| CN109212070B (en) * | 2018-09-24 | 2021-05-07 | 丁立平 | Gas chromatography for simultaneously determining four benzoic acid herbicides in grains |
| CN114705785B (en) * | 2022-04-21 | 2023-11-07 | 厦门泓益检测有限公司 | Method for detecting chlorophthalic acid in vegetable oil |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11352120A (en) * | 1998-04-08 | 1999-12-24 | Shimadzu Corp | Analytical device for polymer material |
| CN104181246A (en) * | 2014-08-25 | 2014-12-03 | 国家烟草质量监督检验中心 | Convergence chromatography analytical method for residue of herbicides in tobacco |
| CN104458947A (en) * | 2014-11-28 | 2015-03-25 | 中国农业科学院烟草研究所 | Method for determining 101 kinds of pesticide residues in tobaccos or tobacco products simultaneously |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003075422A (en) * | 2001-09-05 | 2003-03-12 | Showa Denko Kk | Method and apparatus for analyzing endcrine disruptors |
-
2017
- 2017-03-16 CN CN201710157643.0A patent/CN107045023B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11352120A (en) * | 1998-04-08 | 1999-12-24 | Shimadzu Corp | Analytical device for polymer material |
| CN104181246A (en) * | 2014-08-25 | 2014-12-03 | 国家烟草质量监督检验中心 | Convergence chromatography analytical method for residue of herbicides in tobacco |
| CN104458947A (en) * | 2014-11-28 | 2015-03-25 | 中国农业科学院烟草研究所 | Method for determining 101 kinds of pesticide residues in tobaccos or tobacco products simultaneously |
Non-Patent Citations (3)
| Title |
|---|
| Simultaneous determination of ten herbicides residues in tobacco samples by gel permeation chromatography-gas chromatography;Huiqing Sun et al;《BTAIJ》;20131231;第7卷(第11期);450-455 |
| 在线GPC-GC-MS/MS法直接检测烟叶中的农药残留;罗彦波 等;《烟草科技》;20160930;第49卷(第9期);42-49 |
| 气相色谱_质谱法测定茶叶中29种酸性除草剂的残留量;颜鸿飞 等;《色谱》;20090531;第27卷(第3期);288-293 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107045023A (en) | 2017-08-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102353742B (en) | Method for selectively measuring 7 benzene series in white latex for cigarette through static headspace-gas chromatograph mass spectrum | |
| CN103323547B (en) | GC-MS/MS method used for analyzing organochlorine, pyrethroid, and dinitroaniline pesticide residues in tobacco and tobacco products | |
| CN107045023B (en) | Method that is a kind of while measuring Common Herbicides residual quantity in tobacco | |
| CN103913528B (en) | Quantitative detection method for pyrethriods pesticides in fresh tea | |
| CN102854271A (en) | Method for measuring residues of three phenoxy carboxylic acid pesticides in tobacco and tobacco products | |
| CN103926348A (en) | Analytical method of simultaneously measuring residues of organophosphorus pesticide and pyrethriods pesticide in fresh leaves | |
| CN104569256A (en) | Method for determining three types of isothiazolinone preservatives in water-based glue by adopting liquid chromatography-tandem mass spectrum | |
| CN105738494A (en) | Isotope dilution high resolution chromaticness combination method for simultaneously detecting organic chlorine pesticides and polychlorinated biphenyl in biological sample, and application | |
| CN103308641A (en) | High performance liquid chromatography-tandem mass spectrometry measuring method of three amide herbicides in tobacco and tobacco products | |
| CN103913538B (en) | The quantitative detecting method of organophosphorus insecticide in a kind of tea fresh leaves | |
| CN103293266B (en) | GC-MS/MS (gas chromatography-tandem mass spectrometry) method for analyzing dinitroaniline pesticide residue in tobacco and tobacco product | |
| CN106404958A (en) | Method for quickly detecting contents of plant growth regulators in vegetables | |
| CN109991358A (en) | Measure chloroacetic method in soil | |
| CN106546675B (en) | The quantitative detecting method of Rynaxypyr residual quantity in a kind of tealeaves | |
| CN108020627A (en) | A kind of method that ultra high efficiency closes three kinds of phenoxy carboxylic acid persticide residues in phase chromatography-tandem mass spectrometry measure tobacco | |
| CN108181394A (en) | The method that a kind of extraction-purification Synchronos method measures three kinds of phenoxy carboxylic acid persticide residues in tobacco | |
| CN105158372B (en) | Method for determining urocanic acid and ethyl ester thereof in cosmetics | |
| CN108508130A (en) | A kind of method that ultra high efficiency conjunction phase chromatography-tandem mass spectrum technology splits, measures Chiral pesticide metalaxyl and dimethomorph enantiomer | |
| CN107957467A (en) | A kind of method of lysophosphatidyl choline in separation determination pharmaceutical preparation | |
| CN106950317A (en) | A kind of method for closing the specific aromatic amine that azo dyes discharges in phase chromatographic tandem mass spectrometric determination Cigarette paper | |
| Jiang et al. | Development of a more specific and accurate multiple reaction monitoring method based on GC–EI/MS/MS for simultaneously monitoring and determining 34 kinds of pesticides in Qianjinzhidai pills | |
| CN109765315A (en) | A kind of preparation method and detection method of polyoxin component C | |
| CN109212076B (en) | Method for detecting oxyfluorfen in water by using HPLC-MS/MS method | |
| CN107490650A (en) | The assay method of fat-soluble colouring agent in a kind of ultra performance liquid chromatography tandem mass spectrum detection cigarette paper | |
| CN104483433B (en) | A kind of measure the method for bis-phenol-S in daily necessities |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 550002 No. 2, Beijing Road, Guiyang, Guizhou Patentee after: Guiyang Customs Integrated Technology Center (Guizhou International Travel Health Care Center, Guiyang Customs Port Outpatient Department) Address before: 550002 No. 2, Beijing Road, Guiyang, Guizhou Patentee before: GUIZHOU INSPECTION AND QUARANTINE TECHNOLOGY CENTER |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190402 |