CN102680589B - The method of LC-MS/MS ginseng Pesticide Residues - Google Patents
The method of LC-MS/MS ginseng Pesticide Residues Download PDFInfo
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Abstract
The present invention discloses a kind of method of LC-MS/MS ginseng Pesticide Residues, and it is characterized in that, the method comprises the steps:, and (1) carries out pre-service to samples of Ginseng to be measured; (2) by the residual quantity of one or more agricultural chemicals in LC-MS/MS samples of Ginseng after pretreatment.This assay method is highly sensitive, specificity is strong, accuracy is good, can be used for the mensuration of the multicomponent residual quantity of ginseng or similar medicinal material Pesticides.
Description
Technical field
The present invention relates to the assay method of ginseng Pesticide Residues, be specifically related to the method adopting LC-MS/MS ginseng Pesticide Residues.
Background technology
Pesticide Residue just causes the great attention of international community in early 1960s, the residues of pesticides expert joint conference (JMPR) constituted jointly by FAO (Food and Agriculture Organization of the United Nation) (FAO) and the World Health Organization (WHO) (WHO) regularly proposes maximum maximum permission quantity to Codex Alimentary Commission (CAC) and evaluates, and CAC has worked out maximum residue limit 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, is also the important content in international trade technology barriers.
In recent years, China's Pesticide Residues detection technique development is very fast, existing national standard method adopts more advanced gas chromatography-mass spectrum and Liquid Chromatography-Tandem Mass Spectrometry at present, comprehensive residue control is carried out to food such as fruit, vegetables, Cereals, animal muscle, honey, fruit juice and fruit wine, has related to pesticide species quantity and reach hundreds of remaining kind.China's Chinese crude drug Pesticide Residues determination techniques is started late, and development relatively lags behind." in Chinese Pharmacopoeia 2005 version annex IXQ " persticide residue determination method ", only cover 9 kinds of organic chlorine agriculture chemicals, 12 kinds of organophosphorus insecticides and 3 kinds of pyrethroid pesticides, larger with the residues of pesticides kind gap of monitoring the relevant laws and regulations defined of Chinese medicine natural drug Pesticide Residues in the world, in producing with Chinese medicine natural drug field planting, the present situation of applying pesticides is difficult to coupling, requires larger distance from domestic and international people to green Chinese medicine natural drug.
The detection level how improving China's Chinese medicine Pesticide Residues has become extremely urgent problem.Therefore, the exploitation medicine efficient assay method that particularly ginseng Pesticides multicomponent is residual is badly in need of.
Summary of the invention
In view of the above-mentioned defect of prior art, the invention provides a kind of method adopting liquid chromatography tandom mass spectrometry determination ginseng Pesticide Residues.The method can be used for the examination of ginseng Pesticide Residues, for the standard drafting medicine Pesticide Residues provides technical service.
The present invention is achieved through the following technical solutions:
There is provided a kind of method for measuring ginseng Pesticide Residues, it is characterized in that, the method comprises the steps:
(1) pre-service is carried out to samples of Ginseng to be measured;
(2) by the residual quantity of one or more agricultural chemicals in LC-MS/MS samples of Ginseng after pretreatment.
According to of the present invention one preferred embodiment, described agricultural chemicals comprises organophosphorus insecticide; More preferably, described organophosphorus insecticide agricultural chemicals listed by table 2.
According to of the present invention one preferred embodiment, the pre-service of described samples of Ginseng comprises to purify the step of samples of Ginseng with PSA (N-propyl group ethylenediamine filler) solid phase extraction column.
According to of the present invention one preferred embodiment, the filling quality of described PSA solid phase extraction column is 1000mg/6mL.
According to of the present invention one preferred embodiment, described PSA solid phase extraction column is before use with the pre-drip washing of acetonitrile.
According to a preferred embodiment of the present invention, in described step (1), the pre-service of samples of Ginseng is comprised by acetonitrile solution extraction samples of Ginseng and the step purified by PSA solid phase extraction column.
According to a particularly preferred embodiment of the present invention, the pre-service of samples of Ginseng comprises: precision takes samples of Ginseng powder, adds water, leave standstill, precision adds the acetonitrile solution of acetic acid, jolting, add anhydrous magnesium sulfate and sodium acetate, jolting, centrifugal, get supernatant and be placed in round-bottomed flask, concentrated, concentrate is by the PSA solid phase extraction column with the pre-drip washing of acetonitrile, collect eluent, nitrogen dries up, and adds inner mark solution, filtering membrane, to obtain final product.
According to of the present invention one preferred embodiment, in described step (2), the chromatographic condition of Liquid Chromatography-Tandem Mass Spectrometry is: adopt C18 post, mobile phase is by A phase and B phase composition, and A phase is the methyl alcohol of ammonium formate, B phase is ammonium formate aqueous solution, adopts gradient elution.
Preferably, the particle diameter of described C18 post is 1.7 ~ 5 μm, column internal diameter 2.1 ~ 4.6mm, and column length is 5 ~ 10cm, is more preferably ACQUITYUPLCHSST3 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: 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, in described step (2), the Mass Spectrometry Conditions of Liquid Chromatography-Tandem Mass Spectrometry is: adopt electric spray ion source, positive ion mode, data acquisition is carried out in the mode of dynamically many reflection monitorings, going bunch voltage to be 60 ~ 200 volts, colliding 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 ginseng thus.
The inventive method is be applied to the residual examination and analysb of ginseng Pesticides multicomponent first.The inventive method in the detection that the multicomponent of medicine agricultural chemicals is residual, can effectively exclusive PCR, ensure stablizing of determinand.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 ginseng or similar medicinal material Pesticides.
The inventive method carries out sample introduction analysis by liquid chromatography-tandem mass spectrometry to samples of Ginseng, detects the residual quantity of Multiple Pesticides in ginseng, and analysis cost is low, additionally reduce false positive simultaneously, improves the accuracy of mensuration, has stronger practicality.The detection of the method to ginseng Pesticide Residues has great importance, has good directive significance to gordian techniquies such as new drugs, can be applicable to the many aspects such as new drug development Quality Control.The method effectively can 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.
Accompanying drawing explanation
Fig. 1 is the mass spectrogram of the hybrid standard product solution obtained according to embodiment 1 method;
Fig. 2 is the mass spectrogram of the samples of Ginseng obtained according to embodiment 1 method.
Embodiment
Embodiment 1
1, materials and methods
1.1 key instruments and reagent
API5500 series connection quadrupole mass spectrometer (Applied biosystems), Agilent1290 liquid chromatograph (Agilent company of the U.S.),
r-210/215 type Rotary Evaporators (Switzerland
company), N-EVAPTM111 Nitrogen evaporator (OrganomationAssociates company of the U.S.), MIKRO200R hydro-extractor (German Hettich company), ultrapure water machine (Millipore company of the U.S.).
Standard sample of pesticide (German Dr.Ehrenstorfer company); Acetonitrile, methyl alcohol, ammonium formate are chromatographically pure.PSA solid phase extraction column (Waters, US).
1.2 experimental technique
1.2.1 chromatographic condition
ACQUITYUPLCHSST3 (1.8 μm, 3.0 × 100mm); With the methanol solution of 5mMol ammonium formate for mobile phase A phase, with 5mMol ammonium formate aqueous solution for Mobile phase B phase, flow velocity 0.4ml/min; According to the form below carries out gradient elution:
Table 1, eluent gradient
1.2.2 Mass Spectrometry Conditions
Ion gun is ESI source, electro-spray ionization source; Kapillary goes the mass spectrometry parameters such as a bunch voltage, collision pond energy in table 2.
Table 2, mass spectrometry parameters table
1.2.3 the preparation of standard solution
It is appropriate that precision takes 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 appropriate that precision takes triphenyl (TPP) (Sigma Co., USA) standard items, adds the solution that methyl alcohol is mixed with 100 μ g/mL, as interior mark standard reserving solution.
In right amount, be diluted to the solution of 0.001 ~ 0.1 μ g/mL with vehicle solution as hybrid standard product working solution, wherein the concentration of inner mark solution is 0.01 μ g/mL for the above-mentioned pesticide standard storing solution of accurate absorption and interior mark standard reserving solution respectively.
1.2.4 the preparation of need testing solution
Precision takes samples of Ginseng powder (samples of Ginseng is provided by Huayu Pharmaceutical Co., Ltd, Shanghai) (crossing No. two sieves) 1.5g, be placed in 50ml centrifuge tube, add 10ml water, mixing, place 2 hours, add the acetonitrile solution 15ml of 0.1% acetic acid, violent jolting 1 minute, add 4g anhydrous magnesium sulfate, 1.5g sodium acetate, violent jolting 1 minute again, the centrifugal 3min of 4000 turns/min, get 10ml supernatant, be placed in round-bottomed flask, 40 DEG C are evaporated to about 1ml, be placed in PSA solid phase extraction column (1000mg/6mL, with the pre-drip washing of 10mL acetonitrile before using) on, with acetonitrile wash round-bottomed flask 3 times, each 1mL, cleansing solution is placed on post in the lump, with acetonitrile 15mL wash-out PSA post, collect eluent, nitrogen blows to dry, add 0.01 μ g/mL inner mark solution 1mL, cross 0.22 filter membrane, obtain.
2, result
2.1 measure
The above-mentioned each standard solution sample introduction 5 μ l of accurate absorption, analyzes according to above-mentioned condition sample introduction, drawing standard curve respectively.Another precision draws need testing solution 5 μ l, analyzes according to above-mentioned condition sample introduction, reads corresponding amount, calculate, to obtain final product from typical curve.
2.2 linear relationship
The each 1 μ l of accurate absorption 0.0001 ~ 0.1 μ g/mL standard items mixed solution, sample introduction is analyzed, record each component chromatographic peak area to be measured, with sample introduction concentration for horizontal ordinate (X), peak area is ordinate (Y), carry out regretional analysis, result (see table 4) shows, each component linear relation is good.
Table 4, regression equation, related coefficient, the recovery and detectability
2.3 detectability
Measure the signal to noise ratio (S/N ratio) of low concentration average recovery solution, be 3: 1 computing method detectabilities (see table 4) with signal to noise ratio (S/N ratio), result shows, this method detectability is far below the limit standard of current food service industry.
2.4 precision test
Get the extraction standard product solution of 0.01 μ g/mL, continuous sample introduction 6 times, record peak area, result shows, the RSD value of above-mentioned 70 kinds of standard sample of pesticide 6 sample introduction peak areas is within the scope of 2.7%-10.4%, and precision is good.
2.5 average recovery tests
Sample thief 1.5g, the standard items adding variable concentrations level are respectively appropriate, operate according to method under " preparation of need testing solution " item in accordance with the law, calculate the recovery and corresponding RSD value.Result (see table 4) shows, this method recovery test result is good.
2.6 stability test
Get the sample solution under average recovery test item, every sample introduction analysis in 5 hours, record peak area, result showed, within 0-20 hour, sample solution is basicly stable.
Claims (11)
1. for measuring the method for ginseng Pesticide Residues, it is characterized in that, the method comprises the steps:
(1) pre-service is carried out to samples of Ginseng to be measured, comprise the following steps: precision takes samples of Ginseng powder, adds water, leave standstill, precision adds the acetonitrile solution of acetic acid, jolting, add anhydrous magnesium sulfate and sodium acetate, jolting, centrifugal, get supernatant and be placed in round-bottomed flask, concentrated, concentrate is by PSA solid phase extraction column, collect eluent, nitrogen dries up, and adds inner mark solution, filtering membrane, to obtain final product;
(2) by the residual quantity of one or more agricultural chemicals in LC-MS/MS samples of Ginseng after pretreatment, wherein chromatographic condition is: adopt C
18post, mobile phase is by A phase and B phase composition, and A phase is the methanol solution of the ammonium formate of 5mMol ~ 10mMol for concentration, and B phase is the ammonium formate aqueous solution of 5mMol ~ 10mMol for concentration, adopts gradient elution; Wherein Mass Spectrometry Conditions is: adopt electric spray ion source, positive ion mode, carries out data acquisition in the mode of dynamic multiple-reaction monitoring, and going bunch voltage to be 60 ~ 200 volts, colliding pond energy is 5 ~ 54 volts, retention time 2.62 ~ 9.96 minutes.
2. method according to claim 1, is characterized in that, described agricultural chemicals is selected from organophosphorus insecticide.
3. method according to claim 2, is characterized in that, described 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 filling quality of described PSA solid phase extraction column is 1000mg/6mL.
5. method according to claim 1, is characterized in that, described PSA solid phase extraction column is before use with the pre-drip washing of acetonitrile.
6. method according to claim 1, is characterized in that, described C
18the particle diameter of post is 1.7 ~ 5 μm, column internal diameter 2.1 ~ 4.6mm, and column length is 5 ~ 10cm.
7. method according to claim 6, is characterized in that, described C
18post is ACQUITYUPLCHSST3 post.
8. method according to claim 1, is characterized in that, wherein the concentration of A phase is 5mMol.
9. method according to claim 1, is characterized in that, wherein the concentration of B phase is 5mMol.
10. method according to claim 1, is characterized in that, wherein A: B volume ratio is 5 ~ 95%: 95 ~ 5%.
11. methods according to claim 1, is characterized in that, wherein the flow velocity of mobile phase is 0.3 ~ 0.5ml/min.
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| CN103604880B (en) * | 2013-11-07 | 2015-01-14 | 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 |
| CN110441453B (en) * | 2019-08-14 | 2022-03-15 | 国家烟草质量监督检验中心 | Method for separating and detecting phosphamidon isomers |
| CN115902066A (en) * | 2022-12-08 | 2023-04-04 | 昆明海关技术中心 | Method for detecting various pesticide residues in pseudo-ginseng |
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