CN102692469B - The method of mycotoxin levels in LC-MS/MS ginseng - Google Patents
The method of mycotoxin levels in LC-MS/MS ginseng Download PDFInfo
- Publication number
- CN102692469B CN102692469B CN201110067385.XA CN201110067385A CN102692469B CN 102692469 B CN102692469 B CN 102692469B CN 201110067385 A CN201110067385 A CN 201110067385A CN 102692469 B CN102692469 B CN 102692469B
- Authority
- CN
- China
- Prior art keywords
- ginseng
- post
- samples
- solution
- phase
- 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.)
- Active
Links
Abstract
The present invention discloses the method for mycotoxin levels in a kind of LC-MS/MS ginseng, it is characterized in that, the method comprises the steps:, and (1) carries out pre-service to samples of Ginseng to be measured; (2) content of one or more mycotoxins in samples of Ginseng after pretreatment is measured by liquid chromatography-series winding matter connection spectrometry.This assay method is highly sensitive, specificity is strong, accuracy is good, can be used for the multicomponent residues detecton of mycotoxin in ginseng or similar medicinal material.
Description
Technical field
The present invention relates to the assay method of mycotoxin levels in ginseng, be specifically related to the method adopting mycotoxin levels in LC-MS/MS ginseng.
Background technology
Mycotoxin (Mycotoxin), also claims mycotoxin, is mycetogenetic secondary metabolite, generally has strong toxicity simultaneously and pollutes the high feature of frequency.Due to the parasitism of fungi and the generation of mycotoxin, have a strong impact on the output of crops, reduce agricultural product and feed quality, cause tremendous economic to lose.Human or animal take in polluted by mycotoxin agriculture, livestock products, or by suck and skin contact mycotoxin can cause multiple toxicity symptom.As unreal in caused, emetic, haemorrhage, dermatitis, nervous centralis is impaired, even dead.Animal experiment and EPDML investigation result also confirm, many mycotoxins also can accumulate that rear generation is carcinogenic in vivo, teratogenesis, mutagenesis, parahormone are poisoning, aleucemia etc., cause permanent lesion (see Zhang Yibing etc. to body, detection analysis [M] Beijing of mycotoxin in agricultural product: Chemical Industry Press, 2006).
The mycotoxin that current research is paid close attention to mainly concentrates on aflatoxin (aflatoxin), ochratoxin (OA), vomitoxin (DON), fumonisin (FUM), zearalenone (ZEN), T-2 toxin and patulin (PAT) etc.Along with the further investigation endangered mycotoxin, the public recognizes its serious threat caused social economy and human health gradually, national governments have also all given great concern, the particularly developed country such as European Union and the U.S. to the distribution of mycotoxin in drug and food and detection and especially this have been set to strict limitation regulation.Food aspect, China has put into effect a lot of statutory standards about mycotoxin (see mycotoxin limitation [S] in mycotoxin limitation [S] in GB2715-2005 food and GB2761-2005 food) in succession, but at medicine field, except Chinese Pharmacopoeia has recorded the detection method (see the People's Republic of China's pharmacopeia version [S] in 2010) of aflatoxin, there is no other standards and put into effect.And existing food standard is and detects for single mycotoxin, there is no and detect the residual standard of multicomponent simultaneously and put into effect.
Therefore, the exploitation medicine efficient assay method that particularly mycotoxin multicomponent is residual in ginseng 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 mycotoxin levels in liquid chromatography tandom mass spectrometry determination ginseng.The method can be used for the examination that in ginseng, mycotoxin is residual, provides technical service for drafting the standard of mycotoxin in medicine.
The present invention is achieved through the following technical solutions:
There is provided a kind of method for measuring mycotoxin levels in ginseng, it is characterized in that, the method comprises the steps:
(1) with HLB post, pre-service is carried out to samples of Ginseng to be measured;
(2) by the content of one or more mycotoxins in LC-MS/MS samples of Ginseng after pretreatment.
According to of the present invention one preferred embodiment, described mycotoxin comprises aflatoxin, T-2 toxin, fumonisin B
1, zearalenone, vomitoxin or ochratoxin A; Wherein said aflatoxin comprises AFB
1, AFB
2, AFG
1or AFG
2.
According to of the present invention one preferred embodiment, described HLB post first uses methanol-eluted fractions before pre-service samples of Ginseng, then washes with water.
According to one of the present invention, preferred embodiment the pre-service of described samples of Ginseng comprises extracts samples of Ginseng to be measured with methyl alcohol, and the step of the solution flowing out HLB post also collected by upper HLB post; Or comprise and extract samples of Ginseng to be measured with methyl alcohol, upper HLB post also by methanol-eluted fractions, collects the step of meoh eluate.
According to a particularly preferred embodiment of the present invention, the pre-service of samples of Ginseng comprises: precision takes samples of Ginseng powder, and precision adds methanol solution, ultrasonic process, centrifugal, filter, accurate Aspirate supernatant, dilute with water, shakes up, get the HLB post of the solution after dilution by having handled well, until there is appropriate air to pass through, collects the solution flowing out HLB post, slowly dry up with nitrogen, precision adds methanol solution makes dissolving, to obtain final product; Or methanol-eluted fractions is used after HLB post on sample, collect meoh eluate, after nitrogen slowly dries up, precision adds methanol solution makes dissolving, centrifugal, gets supernatant, to obtain final product.
According to one of the present invention, 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 methyl alcohol, and B phase is formic acid, employing 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 ACQUITYUPLCBEHC18 post; The concentration of B phase is 0.01 ~ 0.05%, preferably 0.01% (volume); A: B volume ratio is 5 ~ 95%: 95 ~ 5%, and preferable flow rate is 0.2 ~ 0.4ml/min, preferred 0.3ml/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, adopt negative ions pattern to carry out data acquisition, going bunch voltage to be-100 ~ 120 volts, colliding pond energy is-48 ~ 53 volts.
The inventive method also comprises the standard items drawing standard curve with various fungimycin, and calculates the content of various fungimycin in samples of Ginseng thus.
The inventive method is be applied to the examination and analysb that in ginseng, mycotoxin multicomponent is residual first.The inventive method in the detection that the multicomponent of medicine mycotoxin 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 multicomponent residues detecton of mycotoxin in ginseng or similar medicinal material.
The inventive method carries out sample introduction analysis by liquid chromatography-tandem mass spectrometry to samples of Ginseng, detects the residual quantity of multiple mycotoxin in ginseng, and analysis cost is low, additionally reduce false positive simultaneously, improves the accuracy of mensuration, has stronger practicality.The method has great importance to the detection that mycotoxin multicomponent in ginseng remains, and has good directive significance, can be applicable to the many aspects such as new drug development Quality Control to gordian techniquies such as new drugs.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 total ion current figure of the hybrid standard product solution (1) of negative ion mode;
Fig. 2 is the total ion current figure of the hybrid standard product solution (2) of negative ion mode;
Fig. 3 is the total ion current figure of the hybrid standard product solution (2) of positive ion mode;
Fig. 4 is the total ion current figure of the need testing solution (1) of negative ion mode;
Fig. 5 is the total ion current figure of the need testing solution (2) of negative ion mode;
Fig. 6 is the total ion current figure of the need testing solution (2) of positive ion mode;
Fig. 7 is the total ion current figure of application of sample recovery need testing solution (1) of negative ion mode;
Fig. 8 is the total ion current figure of application of sample recovery need testing solution (2) of negative ion mode;
Fig. 9 is the total ion current figure of application of sample recovery need testing solution (2) of positive ion mode.
Embodiment
Embodiment 1
1, materials and methods
1.1 key instruments and reagent
API4000 series connection quadrupole mass spectrometer (Applied biosystems), ACQUITYUltraPerformanceLC liquid chromatograph (Waters, US), MIKRO200R hydro-extractor (German Hettich company), ultrapure water machine (Millipore company of the U.S.).
Aflatoxin, T-2 toxin, fumonisin B
1, zearalenone, vomitoxin or ochratoxin A standard items (SUPELCO company of the U.S.); Acetonitrile, formic acid, ammonium formate are chromatographically pure.HLB decontaminating column (Waters company).
1.2 experimental technique
1.2.1 chromatographic condition
ACQUITYUPLCBEHC18 (1.7 μm, 2.1 × 100mm); With 100% methyl alcohol for mobile phase A phase, with 0.01% formic acid for Mobile phase B phase, flow velocity 0.3ml/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
The preparation precision of contrast stock solution takes aflatoxin B1, AFB 2, aflatoxin G 1, AFG 2, T-2 toxin, ochratoxin A, fumonisin B1, zearalenone are vomitted and it is appropriate to tell toxin mark standard items, add the solution that acetontrile becomes 5mg/L, as mixing contrast storing solution.
The preparation of typical curve solution is accurate respectively draws above-mentioned mixing contrast storing solution in right amount, becomes the series mixing contrast solution of concentration described in following table with 50% methanol dilution.
Table 3, series standard solution concentration table
(Hua Yu medicinal material company limited provides separately to get samples of Ginseng powder, respectively according to " Chinese Pharmacopoeia " version annex in 2010, GB/T5009.118-2008, GB/T23502-2009, SN/T1572-2005, GB/T23504-2009, the method inspection that GB/T23503-2009 describes, do not detect aflatoxin B1, AFB 2, aflatoxin G 1, AFG 2, T-2 toxin, ochratoxin A, fumonisin B1, zearalenone and vomitoxin) (crossing No. two sieves) 5g, accurately weighed, " solution flowing out HLB post is collected according to standby being operated to of legal system below following " preparation of need testing solution " item, slowly dry up with nitrogen ", add above-mentioned series standard solution 1ml respectively, as series standard curve solution (1).Use 5ml methanol-eluted fractions HLB post subsequently, collect meoh eluate, slowly dry up with nitrogen, precision adds above-mentioned series standard solution 1ml, as series standard curve solution (2).
1.2.4 the preparation of need testing solution
Precision takes samples of Ginseng powder (Hua Yu medicinal material company limited provides) (crossing No. two sieves) 5g, precision adds 70% methanol solution 50ml, ultrasonic process 30 minutes, centrifugal, filter, accurate Aspirate supernatant 10ml, be diluted with water to 20ml, shake up, solution 5ml after accurate absorption dilution, slow transit through the HLB handled well and (first use methyl alcohol 2ml wash-out, use water 2ml wash-out again) post, until there is appropriate air to pass through, collect the solution flowing out HLB post, slowly dry up with nitrogen, precision adds 50% methyl alcohol 1ml solution makes dissolving, as need testing solution (1), use 5ml methanol-eluted fractions HLB post subsequently, collect meoh eluate, slowly dry up with nitrogen, precision adds 50% methyl alcohol 1ml solution makes dissolving, as need testing solution (2).
2, result
2.1 measure
The above-mentioned series standard curve solution (1) of accurate absorption and each 1 μ l of need testing solution (1) respectively, inject liquid chromatograph-mass spectrometer, measure, by the content of calibration curve method measure and calculation vomitoxin, accurate absorption series standard curve solution (2) and each 1 μ l of need testing solution (2) again, inject liquid chromatograph-mass spectrometer, measure, by calibration curve method measure and calculation aflatoxin B1, AFB 2, aflatoxin G 1, AFG 2, T-2 toxin, fumonisin B1, ochratoxin A, the content of zearalenone, obtain.
2.2 calculate
In formula:
ω---the concentration of often kind of toxin in sample, μ g/kg;
ρ---the concentration of often kind of toxin in the test solution drawn from typical curve, ng/ml;
M---sample volume, g.
Vomitoxin, aflatoxin B1, AFB 2, aflatoxin G 1, AFG 2, T-2 toxin, fumonisin B1, ochratoxin A or zearalenone is not detected in above-mentioned samples of Ginseng.
2.3 linear relationship
The each 1 μ l of the above-mentioned series standard solution of accurate absorption, 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 and related coefficient
2.4 detectability
Measure the signal to noise ratio (S/N ratio) of low concentration average recovery solution, be 3: 1 computing method detectabilities (see table 5) with signal to noise ratio (S/N ratio), result shows, this method detectability is far below the limit standard of current food service industry.
Table 5, detectability
2.5 precision test
Get extraction standard solution 3, continuous sample introduction 6 times, record peak area, result shows, the RSD value of above-mentioned seven kinds of compositions 6 sample introduction peak areas is within the scope of 1.3%-3.1%, and precision is good.
2.6 stability test
Get the sample solution of the intermediate concentration under recovery test item, every sample introduction analysis in 6 hours, record peak area, result showed, within 0-12 hour, sample solution is basicly stable.
2.7 average recovery tests
Get samples of Ginseng powder 5g, the standard items adding variable concentrations level are respectively appropriate, and under product processing item, method operates in accordance with the law in the same old way, calculate the recovery and corresponding RSD value.Result (see table 6) shows, this method recovery test result is good.
Table 6, recovery test (n=9)
Claims (8)
1. for measuring the method for mycotoxin levels in ginseng, it is characterized in that, the method comprises the steps:
(1) carry out pre-service with HLB post to samples of Ginseng to be measured, it comprises and extracts samples of Ginseng to be measured with methyl alcohol, and upper HLB post also collects the step of the solution flowing out HLB post;
(2) by the content of vomitoxin in LC-MS/MS samples of Ginseng after pretreatment, the chromatographic condition of described Liquid Chromatography-Tandem Mass Spectrometry is: adopt C18 post, mobile phase is by A phase and B phase composition, A phase is methyl alcohol, B phase is the formic acid of 0.01 ~ 0.05%, adopt gradient elution, wherein A: B volume ratio gradient elution program is as follows:
2. method according to claim 1, is characterized in that, described HLB post first uses methanol-eluted fractions before pre-service samples of Ginseng, then washes with water.
3. method according to claim 1, is characterized in that, in described step (1), the pre-service of samples of Ginseng to be measured comprises: precision takes samples of Ginseng powder, precision adds methanol solution, ultrasonic process, centrifugal, filter, accurate Aspirate supernatant, dilute with water, shake up, getting the HLB post of the solution after dilution by having handled well, until there is appropriate air to pass through, collecting the solution flowing out HLB post, dry up with nitrogen, precision adds methanol solution makes dissolving; Or methanol-eluted fractions is used after HLB post on sample, collect meoh eluate, after nitrogen dries up, precision adds methanol solution makes dissolving, centrifugal, gets supernatant.
4. method according to claim 1, it is characterized in that, in described step (2), the Mass Spectrometry Conditions of Liquid Chromatography-Tandem Mass Spectrometry is: adopt electric spray ion source, adopt negative ions pattern to carry out data acquisition, going bunch voltage to be-100 ~ 120 volts, colliding pond energy is-48 ~ 53 volts.
5. method according to claim 1, is characterized in that, 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.
6. method according to claim 1, is characterized in that, described C18 post is ACQUITYUPLCBEHC18 post.
7. method according to claim 1, is characterized in that, wherein the concentration of B phase is 0.01%.
8. method according to claim 1, is characterized in that, wherein the flow velocity of mobile phase is 0.2 ~ 0.4ml/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110067385.XA CN102692469B (en) | 2011-03-21 | 2011-03-21 | The method of mycotoxin levels in LC-MS/MS ginseng |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110067385.XA CN102692469B (en) | 2011-03-21 | 2011-03-21 | The method of mycotoxin levels in LC-MS/MS ginseng |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102692469A CN102692469A (en) | 2012-09-26 |
| CN102692469B true CN102692469B (en) | 2016-03-30 |
Family
ID=46858064
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110067385.XA Active CN102692469B (en) | 2011-03-21 | 2011-03-21 | The method of mycotoxin levels in LC-MS/MS ginseng |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102692469B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103344715A (en) * | 2013-06-20 | 2013-10-09 | 中国环境科学研究院 | Method for separation and enrichment of penicillin antibiotics in water |
| CN103543221A (en) * | 2013-09-30 | 2014-01-29 | 王加启 | Method for simultaneously detecting multiple mycotoxins in milk |
| CN103954714B (en) * | 2014-01-03 | 2016-03-30 | 南通市产品质量监督检验所 | A kind of assay method of aflatoxin |
| CN104391057B (en) * | 2014-11-24 | 2016-08-24 | 重庆市动物疫病预防控制中心 | For detecting pretreating reagent box and the application thereof of ochratoxin A in porcine tissue |
| CN107085063A (en) * | 2017-05-26 | 2017-08-22 | 上海市食品药品检验所 | A kind of analysis method of mycotoxin in medicine-food two-purpose kind subclass Chinese medicine |
| CN107153103B (en) * | 2017-06-26 | 2020-04-24 | 四川省农业科学院分析测试中心 | Method for determining contents of various mycotoxins in fresh milk sample |
| CN107860858A (en) * | 2017-11-01 | 2018-03-30 | 上海市食品药品检验所 | A kind of method for high-flux analysis of mycotoxin in plant medicine material |
| CN108426962B (en) * | 2018-05-23 | 2021-01-19 | 华南理工大学 | Method for simultaneously detecting 7 typical mycotoxins in fruits and vegetables |
| CN109828072B (en) * | 2019-02-21 | 2021-06-25 | 安徽润安信科检测科技有限公司 | Method for simultaneously detecting 16 biotoxins in brewing raw materials by using ultra-high performance liquid chromatography-triple quadrupole tandem mass spectrometer |
| CN111879874A (en) * | 2020-08-04 | 2020-11-03 | 山东中医药大学 | Method for determining aflatoxin content in platycladi seeds |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4181853A (en) * | 1976-12-10 | 1980-01-01 | Varian Associates, Inc. | Liquid chromatography system with packed flow cell for improved fluorescence detection |
| CN1645134A (en) * | 2005-01-26 | 2005-07-27 | 上海大学 | Detection for zearalenone |
| CN101109735A (en) * | 2007-05-14 | 2008-01-23 | 劲牌有限公司 | Fluorescence photometry for immune affinity column of aflatoxin in paddy |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100948589B1 (en) * | 2008-03-05 | 2010-03-23 | 한국과학기술원 | Method for assaying mycotoxin |
-
2011
- 2011-03-21 CN CN201110067385.XA patent/CN102692469B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4181853A (en) * | 1976-12-10 | 1980-01-01 | Varian Associates, Inc. | Liquid chromatography system with packed flow cell for improved fluorescence detection |
| CN1645134A (en) * | 2005-01-26 | 2005-07-27 | 上海大学 | Detection for zearalenone |
| CN101109735A (en) * | 2007-05-14 | 2008-01-23 | 劲牌有限公司 | Fluorescence photometry for immune affinity column of aflatoxin in paddy |
Non-Patent Citations (8)
| Title |
|---|
| Airborne molds and mycotoxins associated with handling of corn silage and oilseed cakes in agricultural environment;Caroline Laniera et al;《Atmospheric Environment》;20100531;第44卷(第16期);第1980-1986页 * |
| MS/MS for Tea, Herbal Infusions and the Derived Drinkable Products.《J. Agric. Food Chem》.2010,第58卷(第24期),第12664-12671页. * |
| Multi-residue Screening Method To Quantify Mycotoxins in Aqueous Environmental Samples;JUDITH SCHENZEL et al;《J. Agric. Food Chem》;20100610;第58卷(第12期);第11207-11217页 * |
| Mycoflora and Multimycotoxin Detection in Corn Silage:Experimental Study;DAVID GARON et al;《J. Agric. Food Chem》;20060331;第54卷(第9期);第3479-3484页 * |
| Mycoflora and Mycotoxin Production in Oilseed Cakes during Farm Storage;CAROLINE LANIER et al;《J. Agric. Food Chem》;20090130;第57卷(第4期);第1640-1645页 * |
| Sofie Monbaliu et al.Multimycotoxin UPLC− * |
| 薏苡仁中7种真菌毒素的液相色谱-串联质谱测定法;郑荣 等;《中国卫生检验杂志》;20110210;第21卷(第2期);第318-320页 * |
| 高效液相色谱-串联三重四极杆质谱分析法测定刀豆中黄曲霉毒素G2 、G1 、B2 、B1;许勇 等;《中国卫生检验杂志》;20110110;第21卷(第1期);第41-43页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102692469A (en) | 2012-09-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102692469B (en) | The method of mycotoxin levels in LC-MS/MS ginseng | |
| Moreno-González et al. | Evaluation of hydrophilic interaction liquid chromatography–tandem mass spectrometry and extraction with molecularly imprinted polymers for determination of aminoglycosides in milk and milk-based functional foods | |
| CN102654490A (en) | Method for measuring content of mycotoxins in araliaceae plants by liquid chromatography-tandem mass spectrometry | |
| CN102419354B (en) | General rapid detection method for small molecule poisonous and harmful substances in liquid milk | |
| Maizels et al. | A LC/MS method for the determination of cyanobacteria toxins in water | |
| CN104777249B (en) | The method measuring effective ingredient amygdaloside content in cough syrup of loquat leaf | |
| CN104991019A (en) | Liquid chromatography-tandem mass spectrometry detection method for Geliemine and Koumine in biological sample | |
| CN102854271A (en) | Method for measuring residues of three phenoxy carboxylic acid pesticides in tobacco and tobacco products | |
| CN105021737A (en) | Method for simultaneously detecting content of dicyandiamide and melamine in dairy products | |
| Kara et al. | Arsenic speciation in rice samples for trace level determination by high performance liquid chromatography-inductively coupled plasma-mass spectrometry | |
| CN104155398A (en) | Method for detecting residual quantity of antivirus drug in hairs of livestock and poultry | |
| CN102628844A (en) | Content determining method for trichlorfon in dried fish | |
| CN103033571A (en) | Method for measuring arsenic form in tobacco | |
| CN103926332A (en) | Ultra performance liquid chromatography method for simultaneously determining contents of uridine, guanosine and adenosine in rhizoma pinelliae extract | |
| Chen et al. | Development of a high-performance liquid chromatography method for the simultaneous quantification of four organoarsenic compounds in the feeds of swine and chicken | |
| Dahiya et al. | Development and validation of LC-MS/MS method to determine the residue of veterinary drugs ivermectin, doramectin and moxidectin in milk | |
| CN110068626A (en) | The measuring method of phthalic acid ester in toy for children | |
| CN101644697A (en) | Detection method of IPBC in cosmetics | |
| CN103728380B (en) | A kind of ion liquid abstraction/HPLC detects the method that in aquatic products, fleraxacin is residual | |
| CN102680589B (en) | The method of LC-MS/MS ginseng Pesticide Residues | |
| CN104820042B (en) | A kind of method of cathinone and 4 methyl methcathinone contents in employing high effective liquid chromatography for measuring sample | |
| CN110261529A (en) | It is connected the method for 23 kinds of veterinary drugs in triple level four bars Mass Spectrometer Method milk based on ultra performance liquid chromatography | |
| CN103336080A (en) | Method for simultaneously detecting tetracycline antibiotics in water | |
| CN105929066A (en) | Method for determining andrographolide and dehydroandrographoline in andrographis tablet by using HPLC | |
| CN104991020A (en) | Liquid chromatography-tandem mass spectrometry test method of wilforlide, triptonide, triptolide and tripterine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |