CN102680589A - Liquid chromatogram (LC)-tandem mass spectrometry method for determining pesticide residues in ginseng - Google Patents
Liquid chromatogram (LC)-tandem mass spectrometry method for determining pesticide residues in ginseng Download PDFInfo
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Abstract
The invention discloses an LC-tandem mass spectrometry method for determining pesticide residues in ginseng. The method is characterized by including the following steps: preprocessing ginseng samples to be determined; and determining the residues of one or more kinds of pesticides in the ginseng samples preprocessed through the LC-tandem mass spectrometry method. The LC-tandem mass spectrometry method for determining the pesticide residues in the ginseng is high in sensibility, specificity and accuracy, and is capable of being used for multi-component residue determination of pesticides in the ginseng or similar crude drugs.
Description
Technical field
The present invention relates to the assay method of persticide residue in the genseng, be specifically related to adopt the liquid chromatography-tandem mass spectrometry method to measure the method for persticide residue in the genseng.
Background technology
The residues of pesticides problem just causes the great attention of international community in early 1960s; Residues of pesticides expert's joint conference (JMPR) by FAO (Food and Agriculture Organization of the United Nation) (FAO) and The World Health Organization (WHO) constitute jointly is regularly estimated the maximum residual quantity that allows of the international food code council (CAC) proposition, and CAC has worked out the MRL standard based on EVALUATION DATA.This standard is the important indicator of test China's Agricultural (comprising Chinese medicine, crude drug medicinal material) quality safety, also is the important content in the international trade technology barriers.
In recent years; The Detecting Pesticide technical development is very fast in China's food; Existing national standard method adopts advanced at present gas chromatography-mass spectrum and liquid chromatography-tandem mass spectrometry method; Food such as fruit, vegetables, Cereals, animal muscle, honey, fruit juice and fruit wine have been carried out the residual control of comprehensive farming, related to pesticide species quantity and reach hundreds of surplus kinds.The residues of pesticides determination techniques is started late in China's Chinese crude drug, and development relatively lags behind." 9 kinds of organic chlorine agriculture chemicals, 12 kinds of organophosphorus insecticides and 3 kinds of pyrethroid pesticides have only been contained among Chinese pharmacopoeia version in 2005 the appendix IX Q " persticide residue determination method "; Bigger with the residues of pesticides kind gap of in the world the relevant laws and regulations defined of residues of pesticides in the Chinese medicine natural drug being monitored; Be difficult to coupling with the present situation of applying pesticides in the production of Chinese medicine natural drug field planting, the requirement of green Chinese medicine natural drug had than big distance from domestic and international people.
The detection level that how to improve residues of pesticides in China's Chinese medicine has become extremely urgent problem.Therefore, be badly in need of the particularly residual efficient measurement method of agricultural chemicals multicomponent in the genseng of exploitation medicine.
Summary of the invention
In view of the above-mentioned defective of prior art, the present invention provides a kind of method that adopts persticide residue in the liquid chromatography tandom mass spectrometry determination genseng.This method can be used for the examination of persticide residue in the genseng, and the standard of residues of pesticides provides technical service in the medicine in order to draft.
The present invention realizes through following technical scheme:
A kind of method that is used for measuring the genseng persticide residue is provided, it is characterized in that, this method comprises the steps:
(1) samples of Ginseng to be measured is carried out pre-service;
(2) pass through the residual quantity that the liquid chromatography-tandem mass spectrometry method is measured one or more agricultural chemicals in pretreated samples of Ginseng.
According to of the present invention one preferred embodiment, said agricultural chemicals comprises organophosphorus insecticide; More preferably, said organophosphorus insecticide is the listed agricultural chemicals of table 2.
According to of the present invention one preferred embodiment, the pre-service of said samples of Ginseng comprises the step with PSA (N-propyl group ethylenediamine filler) solid phase extraction column purifying samples of Ginseng.
According to of the present invention one preferred embodiment, the filling quality of said PSA solid phase extraction column is 1000mg/6mL.
According to of the present invention one preferred embodiment, said PSA solid phase extraction column is washed with the acetonitrile pre-leaching before use.
According to a preferred embodiment of the present invention, the pre-service of samples of Ginseng comprises the step of extracting samples of Ginseng and purifying through the PSA solid phase extraction column with acetonitrile solution in the said step (1).
Especially preferred embodiment the pre-service of samples of Ginseng comprises: precision takes by weighing the samples of Ginseng powder, adds water according to one of the present invention, leaves standstill, the accurate acetonitrile solution that adds acetate; Jolting adds anhydrous magnesium sulfate and sodium acetate, and jolting is centrifugal; Get supernatant and place round-bottomed flask, concentrate, the PSA solid phase extraction column of concentrate through washing with the acetonitrile pre-leaching collected eluent; Nitrogen dries up, and adds inner mark solution, and filtering membrane promptly gets.
According to of the present invention one preferred embodiment, the chromatographic condition of liquid chromatography-tandem mass spectrometry method is in the said step (2): adopt the C18 post, moving phase by A mutually with the B phase composition, A is the methyl alcohol of ammonium formate mutually, B is the ammonium formate WS mutually, the employing gradient elution.
Preferably, the particle diameter of said C18 post is 1.7～5 μ m, and column internal diameter 2.1～4.6mm, column length are 5～10cm, more preferably ACQUITY UPLC HSS T3 post; The concentration of A phase is 5mMol～10mMol, preferred 5mMol (molal weight), and the concentration of B phase is 5mMol～10mMol, preferred 5mMol (molal weight); A: the B volume ratio is 5～95%: 95～5%, and preferable flow rate is 0.3～0.5ml/min, more preferably 0.4ml/min.
According to of the present invention one preferred embodiment; The mass spectrum condition of liquid chromatography-tandem mass spectrometry method is in the said step (2): adopt electric spray ion source; Positive ion mode; Modes with dynamically many reflection monitorings are carried out data acquisition, and to remove bunch voltage be 60～200 volts, collide the pond energy is 5～54 volts, retention time 2.62～9.96 minutes.
The inventive method also comprises the standard items drawing standard curve with various agricultural chemicals, and calculates the content of various agricultural chemicals in the genseng thus.
The inventive method is for be applied to residual detection and the analysis of agricultural chemicals multicomponent in the genseng first.The inventive method can effectively be got rid of interference, guarantee the stable of determinand in the residual detection of the multicomponent of medicine agricultural chemicals.This determination and analysis method is highly sensitive, specificity is strong, accuracy good, can be used for the mensuration of the multicomponent residual quantity of agricultural chemicals in genseng or the similar medicinal material.
The inventive method is carried out the sample introduction analysis through liquid chromatography-tandem mass spectrometry to samples of Ginseng, detects the residual quantity of Multiple Pesticides in the genseng, and analysis cost is low, reduced false positive again simultaneously, improved the accuracy of measuring, and stronger practicality is arranged.This method has great importance to the detection of persticide residue in the genseng, and gordian techniquies such as new drug are had good directive significance, can be applicable to many aspects such as new drug development Quality Control.This method can effectively be applied to the formulation of national standard, the research and development of enterprise's new drug, the lifting of enterprise's existing product quality control method.
Description of drawings
Fig. 1 is the mass spectrogram of the hybrid standard article solution that obtains according to embodiment 1 method;
Fig. 2 is the mass spectrogram of the samples of Ginseng that obtains according to embodiment 1 method.
Embodiment
Embodiment 1
1, materials and methods
1.1 key instrument and reagent
API 5500 series connection quadrupole mass spectrometers (u.s.a. applied biosystem company); Agilent 1290 liquid chromatographs (U.S. Agilent company);
R-210/215 type Rotary Evaporators (Switzerland
company); N-EVAPTM111 Nitrogen evaporator (U.S. Organomation Associates company); MIKRO 200R hydro-extractor (German Hettich company), ultrapure water machine (U.S. Millipore company).
Standard sample of pesticide (German Dr.Ehrenstorfer company); Acetonitrile, methyl alcohol, ammonium formate are chromatographically pure.PSA solid phase extraction column (U.S. Waters company).
1.2 experimental technique
1.2.1 chromatographic condition
ACQUITY UPLC HSS T3 (1.8 μ m, 3.0 * 100mm); Methanol solution with the 5mMol ammonium formate is the mobile phase A phase, is the Mobile phase B phase with the 5mMol ammonium formate WS, flow velocity 0.4ml/min; According to the form below carries out gradient elution:
Table 1, eluent gradient
1.2.2 mass spectrum condition
Ion gun is ESI source, electro-spray ionization source; Kapillary goes mass spectrum parameters such as a bunch voltage, collision pond energy to see table 2.
Table 2, mass spectrum parameter list
1.2.3 the preparation of standard solution
It is an amount of that precision takes by weighing each standard sample of pesticide, adds the solution that methyl alcohol is mixed with 100 μ g/mL, as each pesticide standard storing solution.
It is an amount of that precision takes by weighing triphenyl (TPP) (U.S. Sigma company) standard items, adds the solution that methyl alcohol is mixed with 100 μ g/mL, as interior mark standard reserving solution.
Accurate respectively above-mentioned pesticide standard storing solution of absorption and interior mark standard reserving solution are an amount of, and the solution that is diluted to 0.001～0.1 μ g/mL with blank matrix solution is as hybrid standard article working solution, and wherein the concentration of inner mark solution is 0.01 μ g/mL.
1.2.4 the preparation of need testing solution
Precision takes by weighing samples of Ginseng powder (samples of Ginseng is provided by Huayu Pharmaceutical Co., Ltd, Shanghai) (crossing sieve No. two) 1.5g, places the 50ml centrifuge tube, adds 10ml water, and mixing was placed 2 hours; The acetonitrile solution 15ml that adds 0.1% acetate, shaken 1 minute adds the 4g anhydrous magnesium sulfate, the 1.5g sodium acetate; Shaken is 1 minute again, and the centrifugal 3min of 4000 commentaries on classics/min gets the 10ml supernatant, places round-bottomed flask; 40 ℃ are evaporated to about 1ml, place on the PSA solid phase extraction column (1000mg/6mL washes with the pre-leaching of 10mL acetonitrile before using), wash round-bottomed flask 3 times with acetonitrile; Each 1mL, cleansing solution places on the post in the lump, with acetonitrile 15mL wash-out PSA post, collects eluent; Nitrogen blows to doing, and adds 0.01 μ g/mL inner mark solution 1mL, crosses 0.22 filter membrane, promptly gets.
2, result
2.1 measure
Above-mentioned each the standard solution sample introduction 5 μ l of accurate respectively absorption analyze the drawing standard curve according to above-mentioned condition sample introduction.The accurate in addition need testing solution 5 μ l that draw analyze according to above-mentioned condition sample introduction, read corresponding amount from typical curve, calculate, and promptly get.
2.2 linear relationship
Accurate each the 1 μ l of 0.0001～0.1 μ g/mL standard items mixed solution that draws, each component chromatographic peak area to be measured is write down in the sample introduction analysis; With sample introduction concentration is horizontal ordinate (X), and peak area is ordinate (Y), carries out regretional analysis; Result's (seeing table 4) shows that each component lines sexual intercourse is good.
Table 4, regression equation, related coefficient, the recovery and detectability
2.3 detectability
Measuring the signal to noise ratio (S/N ratio) of low concentration average recovery solution, is 3: 1 computing method detectabilities (seeing table 4) with signal to noise ratio (S/N ratio), and the result shows that this method detectability is far below the limit standard of present food service industry.
2.4 precision test
Get the matrix standard solution of 0.01 μ g/mL, continuous sample introduction 6 times, the record peak area, the result shows that the RSD value of 6 sample introduction peak areas of above-mentioned 70 kinds of standard sample of pesticide is in the 2.7%-10.4% scope, precision is good.
2.5 average recovery test
Sample thief 1.5g, the standard items that add the variable concentrations level respectively are an amount of, operate calculate recovery rate and corresponding RSD value according to method under " preparation of need testing solution " item in accordance with the law.Result's (seeing table 4) shows that the result is good for this method recovery test.
2.6 stability test
Get the sample solution under the average recovery test item, every at a distance from sample introduction analysis in 5 hours, the record peak area, the result shows that within 0-20 hour, sample solution is basicly stable.
Claims (18)
1. be used for measuring the method for genseng persticide residue, it is characterized in that, this method comprises the steps:
(1) samples of Ginseng to be measured is carried out pre-service;
(2) pass through the residual quantity that the liquid chromatography-tandem mass spectrometry method is measured one or more agricultural chemicals in pretreated samples of Ginseng.
2. method according to claim 1 is characterized in that said agricultural chemicals is selected from organophosphorus insecticide.
3. method according to claim 2; It is characterized in that said organophosphorus insecticide is selected from triazotion, methyl azinphos-methyl, cadusafos, chlorfenviphos, chlopyrifos, chlorpyrifos-methyl, Resistox, Ruelene, cyanofenphos, demeton-methyl sulfone, dialifos, diazinon, Carbicron, Rogor, dioxathion, disulfoton, disulfoton sulfone, disulfoton sulfoxide, edifenphos, Ethodan, ethoprop, fenamiphos, fenamiphos sulfone, fenamiphos sulfoxide, oxygen Nankor, fenifrothion, fensulfothion, oxygen fensulfothion, oxygen fensulfothion sulfone, fensulfothion sulfone, Entex, oxygen Entex, oxygen Entex sulfone, oxygen Entex sulfoxide, Entex sulfone, Entex sulfoxide, Fonofos, lythidathion, isofenphos, malaoxon, malathion, Afos, methacrifos, acephatemet, methidathion, Menite, Azodrin, flolimat, metilomerkaptofosoksid, paraoxon, methyl paraoxon, parathion, parathion-methyl, phenthoate dimephenthoate cidial, thimet, oxygen thimet, oxygen thimet sulfone, thimet sulfone, Phosalone, phosphamidon, phoxim, Diothyl, pirimiphos-methyl, Profenofos, the phonetic phosphorus of pyrrole, quinalphos, tolelofos-methyl, Hostathion, De-Green or menazon.
4. method according to claim 1 is characterized in that, the pre-service of samples of Ginseng comprises the step with PSA solid phase extraction column purifying samples of Ginseng in the said step (1).
5. method according to claim 4 is characterized in that, the filling quality of said PSA solid phase extraction column is 1000mg/6mL.
6. method according to claim 4 is characterized in that, said PSA solid phase extraction column is washed with the acetonitrile pre-leaching before use.
7. method according to claim 1 is characterized in that, the pre-service of samples of Ginseng comprises the step of extracting samples of Ginseng and purifying through the PSA solid phase extraction column with acetonitrile solution in the said step (1).
8. method according to claim 1 is characterized in that, the pre-service of samples of Ginseng may further comprise the steps in the said step (1): precision takes by weighing the samples of Ginseng powder, adds water, leaves standstill; The accurate acetonitrile solution that adds acetate, jolting adds anhydrous magnesium sulfate and sodium acetate, and jolting is centrifugal; Get supernatant and place round-bottomed flask, concentrate, concentrate is collected eluent through the PSA solid phase extraction column; Nitrogen dries up, and adds inner mark solution, and filtering membrane promptly gets.
9. method according to claim 1 is characterized in that, the chromatographic condition of liquid chromatography-tandem mass spectrometry method is in the said step (2): adopt C
18Post, moving phase is by A phase and B phase composition, and A is the methanol solution of ammonium formate mutually, and B is the ammonium formate WS mutually, adopts gradient elution.
10. method according to claim 1; It is characterized in that; The mass spectrum condition of liquid chromatography-tandem mass spectrometry method is in the said step (2): adopt electric spray ion source, positive ion mode carries out data acquisition with the mode of dynamic multiple-reaction monitoring; Removing bunch voltage is that 60～200 volts, collision pond energy are 5～54 volts, retention time 2.62～9.96 minutes.
11. method according to claim 9 is characterized in that, said C
18The particle diameter of post is 1.7～5 μ m, and column internal diameter 2.1～4.6mm, column length are 5～10cm.
12. method according to claim 11 is characterized in that, said C
18Post is an ACQUITY UPLC HSS T3 post.
13. method according to claim 9 is characterized in that, wherein the concentration of A phase is 5mMol～10mMol.
14. method according to claim 13 is characterized in that, wherein the concentration of A phase is 5mMol.
15. method according to claim 9 is characterized in that, wherein the concentration of B phase is 5mMol～10mMol.
16. method according to claim 15 is characterized in that, wherein the concentration of B phase is 5mMol.
17. method according to claim 9 is characterized in that, wherein A: the B volume ratio is 5～95%: 95～5%.
18. method according to claim 9 is characterized in that, wherein the flow velocity of moving phase is 0.3～0.5ml/min.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103604880A (en) * | 2013-11-07 | 2014-02-26 | 同济大学 | Method for detecting triazophos pesticide in environmental samples of different types |
| CN105116064A (en) * | 2015-07-17 | 2015-12-02 | 中国农业科学院茶叶研究所 | Automatic sample pretreatment and detection method for detecting residual of multiple pesticides in tea leaves |
| CN110441453A (en) * | 2019-08-14 | 2019-11-12 | 国家烟草质量监督检验中心 | A kind of method of separation detection phosphamidon isomers |
| NL2034552A (en) * | 2022-12-08 | 2023-04-26 | Technical Center Of Huangpu Customs | Rapid method for detecting multi-pesticide residues in panax notoginseng |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103604880A (en) * | 2013-11-07 | 2014-02-26 | 同济大学 | Method for detecting triazophos pesticide in environmental samples of different types |
| CN105116064A (en) * | 2015-07-17 | 2015-12-02 | 中国农业科学院茶叶研究所 | Automatic sample pretreatment and detection method for detecting residual of multiple pesticides in tea leaves |
| CN110441453A (en) * | 2019-08-14 | 2019-11-12 | 国家烟草质量监督检验中心 | A kind of method of separation detection phosphamidon isomers |
| NL2034552A (en) * | 2022-12-08 | 2023-04-26 | Technical Center Of Huangpu Customs | Rapid method for detecting multi-pesticide residues in panax notoginseng |
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