CN103969364A - Method for measuring seven fungaltoxin in fodder and cereal through liquid chromatogram tandem mass spectrometry - Google Patents
Method for measuring seven fungaltoxin in fodder and cereal through liquid chromatogram tandem mass spectrometry Download PDFInfo
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Abstract
The invention relates to a method for measuring seven fungaltoxin in fodder and cereal through liquid chromatogram tandem mass spectrometry. The related seven fungaltoxin are DON, D3G, NIV, 3ADON, 15ADON, FUSX and DOM. According to the method, the modified dispersive solid-phase extraction method is adopted to remove lipid and other interfering substances in a sample, and then qualitative and quantitative analysis is performed on the processed sample through a liquid chromatogram tandem triple quadrupole mass spectrometer. The method has the following advantages: the sample pretreatment is simple, rapid, economical, short in parsing time, high in sensitivity and recovery rate, and excellent in repeatability and specificity; the method is applicable to detecting multicomponent fungaltoxin in fodder and cereal samples and provides effective technological support for ensuring safety of fodder and cereal of China.
Description
Technical field
The present invention relates to mycotoxin method for measuring in feed and cereal, be specifically related to adopt Liquid Chromatography-Tandem Mass Spectrometry method to measure the method for 7 kinds of mycotoxins in feed and cereal.
Background technology
Mycotoxin (Mycotoxin) is by mycetogenetic secondary metabolite.Their pollution condition in crop products, food and feeds are on the rise, and the health of humans and animals has been caused to great harm.Wherein, category-B Trichothecenes toxin is the highest class mycotoxin of incidence in global range.It is produced and extensively polluted cereal such as wheat, barley, corn and products thereof by sickle-like bacteria.This toxoid mainly comprises 5 kinds: deoxynivalenol (DON); nivalenol (NIV); 3-acetyl group deoxynivalenol (3ADON), 15-acetyl group deoxynivalenol (15ADON) and fusarenon-X (FUSX).
The symptoms such as DON can cause animal food refusal, vomiting, feels sick, growthing lag, neuroendocrine disturbance and immunosupress.Simultaneously, it also has very strong cytotoxicity (inhibition DNA, RNA, protein synthesize), embryotoxicity (embryonic death, growth retardation of fetus, functional development are incomplete), certain teratogenesis, weak carcinogenicity, and affects the immune system of humans and animals.3ADON and 15ADON are the acetylized compounds of DON.Compared to the toxicity of DON, these two kinds of toxin have similar even higher toxicity.Research shows, these two kinds of toxin in animal body can deacetylated formation DON, increased potentially the intake of DON.At present less about the toxicologic study of NIV and FUSX.But can there is slight pathological change containing the feed of NIV in a few studies discovery broiler feeding 1mg/kg, the 5mg/kg that feeds does not have obvious pathology containing the feed of DON.
Some mycotoxin can be in conjunction with the stronger material of some polarity, as sugar, amino acid, sulfate etc. under the effect of plant endoenzyme.These toxin conventionals method of analysis in conjunction with state can't detect conventionally, are therefore called as hidden-type mycotoxin.Deoxynivalenol-3-glucoside (D3G) is to report in recent years maximum hidden-type toxin, and it is extensively found in grain class and beer fermentation liquid.Research shows, D3G toxicity is lower, but after taking in, it can be hydrolyzed to DON toxin monomer and bring into play toxic action humans and animals under the effect of microorganism in vivo, and in feed, the pollution condition of hidden-type DON is not also reported at present.Due to the potential health risk of D3G, it has caused that people greatly pay close attention to.In addition, decylization oxygen-deoxynivalenol (DOM) is DON main metabolites in vivo.In natural cereals, be not also found.Consider that animal derived tissue may be added in feed as protein source, DOM is also necessary to detect.
European Union has promulgated that in 2006 the suggestion Limited Doses of pig feed and feed DON in cereal is respectively 900 μ g/kg and 8000 μ g/kg; China is within 2007, having promulgated DON limit standard in mixed feed " allowance of deoxynivalenol in GB13078.3-2007 mixed feed " regulation: in swine feed, calf mixed feed and lactation period animal mixed feed, maximum limitation is 1000 μ g/kg, and in ox mixed feed and poultry mixed feed, maximum limitation is 5000 μ g/kg.In addition, in the 72nd meeting that the food additives joint specialist council of FAO (Food and Agriculture Organization of the United Nation)/World Health Organization (WHO) (JECFA) is to hold for 2010, the limit standard that comprises DON, 3ADON and 15ADON toxin total amount is formulated in suggestion.D3G is thought that by JECFA potential DON takes in source simultaneously.For NIV, FUSX, owing to lacking relevant toxicologic study, does not also formulate relevant limit standard at present.
In cereal and food, the detection method of category-B Trichothecenes toxin and D3G has had report at present: " Journal of agricultural and food chemistry ", 2012,46,11638 and " Mycotoxinresearch ", 2012,28,181 measure DON in cereal, corn and products thereof by liquid phase tandem mass spectrometry after multi-functional MycoSep226 or 225 column purifications, D3G, the content of 3ADON and 15ADON.This class methods pre-treatment complex operation and cost are higher, and to the D3G recovery (50%-60%) on the low side; " Foodadditives and contaminants:Part A ", does not purify direct liquid phase tandem mass spectrometry and measures DON and D3G content in wheat and maize after 2009,26,507 sample extraction.Although the method pre-treatment simple and fast, the interfering materials such as the lipid containing in sample seriously lower detection sensitivity, and long-term use caused very big damage to mass ion source.
In feed, the pollution condition of hidden-type DON and category-B trichothecene same clan mycotoxin is not also reported at present.Meanwhile, the method for existing this type of mycotoxin of detection mainly concentrates on food and cereals, does not comprise animal feed.In order to ensure feed safety and animal production efficiency, be necessary to set up effective and reliable analytical approach and monitor its generation and pollution condition.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, and provide that a kind of pre-treating method simple economy is quick, method that sensitivity and the high liquid phase tandem mass spectrometry of accuracy are measured feed and the cereal ZhongBLei trichothecene same clan and hidden-type DON.
To achieve these goals, the present invention has adopted following technical scheme, specifically comprises the steps:
(1) accurately take sample 2g (being accurate to 0.01g) and be placed in 50mL centrifuge tube, add 8mL acetonitrile/water solution (84/16, v/v).After vortex vibration 2min, ultrasonic extraction 0.5h.Then centrifugal 5min under 4000r/min, gets 2mL supernatant to be clean.
(2) 2mL supernatant is transferred in 15mL taper centrifuge tube, then adds 100mg anhydrous magnesium sulfate and 1mL normal hexane, after violent vortex 1min under 4000r/min centrifugal 5min, normal hexane layer is removed.Remaining solution nitrogen at 40 DEG C dries up, and adds the violent vortex of 500 μ L ammonium acetate aqueous solutions (5mM), and it is to be analyzed that final sample solution is crossed 0.22 μ m nylon leaching film.
(3) detected sample step (2) being obtained is analyzed by Liquid Chromatography-Tandem Mass Spectrometry instrument, obtains respectively the result of the trichothecene same clan of B family and D3G residual quantity.
(4) the liquid phase analysis condition using in step (3) is specific as follows:
Chromatographic column: Agilent Extend-C18column (150mm × 3.0mm, 3.5 μ m), column temperature: 40 DEG C, flow velocity: 0.3mL/min, sample size: 5 μ L;
Mobile phase: A phase: 5mM ammonium acetate aqueous solution, B phase: methyl alcohol;
Gradient elution program: 0-1min, 20%B; 1-5min, 90%B, 5-6min90%B, 6-6.5min, 20%B, 6.5-8min20%B;
(5) the mass spectrophotometry condition using in step (3) is specific as follows:
Ion gun pattern: negative ions pattern (ESI
+and ESI
-); Spray voltage: 4.5kv (ESI
+) and-3.5ky (ESI
-); Heat block temperature: 400 DEG C; Ion transfer tube temperature: 250 DEG C; Atomization gas and dry gas flow velocity: 3mL/min and 15mL/min; The mass spectrum parameter of 7 kinds of mycotoxins is in table 1.
The mass spectrum parameter of the each mycotoxin of table 1
Note; *, quota ion;
a, qualitative abundance of ions and quota ion abundance number percent;
The present invention compared with prior art, has following technological merit and effect: pre-treatment adopts improved dispersion solid phase extraction.Compared with general Solid-Phase Extraction method, the method is more simple and efficient, time and the cost of having saved sample preparation, the consumption that has reduced organic solvent.Sample after treatment is very clean simultaneously, and after continuous sample introduction, sensitivity does not have significant change, and the mass spectrometric ion gun of triple level Four bars still keeps clean.D3G is had to the satisfied recovery (85%).In the inventive method, the quantitative limit of different mycotoxins in different substrates is respectively: DON, 5.0-7.8 μ g/kg; NIV, 8.4-12.6 μ g/kg; D3G, 5.5-8.4 μ g/kg; 3ADON, 5.3-8.8 μ g/kg; 15ADON, 5.3-10.0 μ g/kg; FUSX, 8.3-13.6 μ g/kg; The recovery is between 80%-118%, and relative standard deviation is between 2.73%-18.39%.Draw thus, sensitivity and precision are apparently higher than the analytical approach of having reported.
Brief description of the drawings
Below in conjunction with drawings and Examples, the present invention is described in more detail
Fig. 1 be 7 kinds of mycotoxin standard solution selection reaction monitoring (SRM) collection of illustrative plates (DON, NIV, 3ADON, 15ADON and FUSX, concentration is 100ng/mL; DOM and D3G, concentration is 75ng/mL);
Selection reaction monitoring (SRM) collection of illustrative plates of the positive sample of Fig. 2;
Fig. 3 is the clean-up effect (a) of different purification methods on 7 kinds of mycotoxins and the impact (b) of the recovery;
Fig. 4 is the matrix effect (b) after the matrix effect (a) of 7 kinds of mycotoxins in different substrates and Isotopic Internal Standard calibration.
Embodiment
The present invention is further illustrated for embodiment given below.The present invention is described in conjunction with most preferred embodiment, but is reading after example of the present invention, and those skilled in the art can understand and in disclosed enforcement, make many changes and also can obtain same or similar result, all belong to the spirit and scope of the present invention.In particular, the alternative reagent disclosed herein of some reagent and obtain identical or similar results.All similar replacements or modification are all considered to the spirit and scope of the present invention, and all above-mentioned equivalent form of values all belong to the scope that the claims in the present invention book limits.
Embodiment 1
1, materials and methods
1.1 key instruments and reagent
Liquid Chromatography-Tandem Mass Spectrometry instrument (LC-MS/MS) (Thermo company of the U.S.);
High speed disintegrator (Yanshan Mountain, Beijing Zheng De plant equipment company limited);
Vortex instrument (its Lindberg Optic Design A/S of Haimen), ultrasonator (Ningbo Xin Zhi company);
Supercentrifuge (Changsha Xiang Yi company), Nitrogen evaporator (upper Haiquan island company);
Milli-Q ultrapure water machine (German Millipore company);
1.2 standard items and reagent
Deoxynivalenol (DON), nivalenol (NIV), 3-acetyl group deoxynivalenol (3ADON), 15-acetyl group deoxynivalenol (15ADON) and fusarenon-X (FUSX) (Sigma company of the U.S.); Deoxynivalenol-3-glucoside (D3G), decylization oxygen-deoxynivalenol (DOM) and Isotopic Internal Standard thing [
13c
15]-DON (Austrian Romerlab company); Graphon (GCB), N-propyl group ethylenediamine adsorbent (PSA), cleanert silica gel, the sorbing materials such as C18 (Tianjin Agela company).
2, experimental technique
2.1 sample-pretreating method
(1) accurately take sample 2g (being accurate to 0.01g) and be placed in 50mL centrifuge tube, add 8mL acetonitrile/water solution (84/16, v/v).After vortex vibration 2min, ultrasonic extraction 0.5h.Then centrifugal 5min under 4000r/min, gets 2mL supernatant to be clean.
(2) 2mL supernatant is transferred in 15mL taper centrifuge tube, then adds 100mg anhydrous magnesium sulfate and 1mL normal hexane, after violent vortex 1min under 4000r/min centrifugal 5min, normal hexane layer is removed.Remaining solution nitrogen at 40 DEG C dries up, first add add again after the violent vortex of 480 μ L ammonium acetate aqueous solutions (5mM) 20 μ L Isotopic Internal Standard things [
13c
15]-DON (1 μ g/mL), it is to be analyzed that final sample solution is crossed 0.22 μ m nylon leaching film.
(3) detected sample obtaining is analyzed by Liquid Chromatography-Tandem Mass Spectrometry instrument, obtains respectively the result of the trichothecene same clan of B family and D3G residual quantity.
2.2 liquid chromatography mass conditions
(1) liquid-phase condition: chromatographic column be Agilent Extend-C18column (150mm × 3.O mm, 3.5 μ m); Taking 5mM ammonium acetate aqueous solution (A) and methyl alcohol (B) as mobile phase, flow velocity is that 0.3mL/min carries out gradient elution, and elution program is as shown in table 2 below:
Table 2 eluent gradient elution program
(2) mass spectrum condition: ion gun pattern: negative ions pattern (ESI
+and ESI
-); Spray voltage: 4.5kv (ESI
+) and-3.5ky (ESI
-); Heat block temperature: 400 DEG C; Ion transfer tube temperature: 250 DEG C; Atomization gas and dry gas flow velocity: 3mL/min and 15mL/min; The mass spectrum parameter of 7 kinds of mycotoxins is in table 3.
The mass spectrum parameter of the each mycotoxin of table 3
Note: *, quota ion;
a, qualitative abundance of ions and quota ion abundance number percent;
3, result and discussion
The optimization of 3.1 different mycotoxin mass spectrum conditions
Under different mobile phase conditions, (A phase: 0.05% ammonia spirit or 5mM ammonium acetate aqueous solution) optimizes the mass spectrum parameter of each mycotoxin.Result shows under 0.05% ammoniacal liquor condition, the relative ion ratio of NIV and 15ADON (qualitative abundance of ions and quota ion abundance number percent) extremely low (as shown in table 4), and this has affected detection sensitivity greatly; On the contrary, under 5mM ammonium acetate solution condition, the ion ratio of all mycotoxins is all greater than 25, and the sensitivity that adds ammonium acetate greatly to improve each mycotoxin in aqueous solution is described.Therefore, 5mM ammonium acetate solution and methyl alcohol are selected as final mobile phase.In addition, 3ADON and 15ADON are isomers.Cannot separate this two kinds of compounds by existing chromatographic equipment, and these two kinds of compounds produce identical molion in ionization process.In order better to distinguish these two kinds of compounds, the quick switch mode of negative ions is used.Result shows that this method can well be distinguished and accurate quantitative analysis 3ADON and 15ADON.
The mass spectrum parameter of table 4 each mycotoxin under 0.05% ammoniacal liquor condition
The optimization of 3.2 pre-treating methods
Method of the present invention has been investigated different dispersion solid extracting agents (GCB, PSA, cleanert silica, C18 etc.) and the clean-up effect of normal hexane to sample.Result shows anhydrous MgSO
4+ GCB adsorbent can be removed pigment in sample makes sample cleaner, but NIV, the recovery (< 70%) on the low side of DON and D3G.Anhydrous MgSO in addition
4+ PSA (or cleanert silica, C18) has greatly improved to the sensitivity of the each mycotoxin in different substrates, but the recovery of D3G undesirable (< 60%).Therefore, anhydrous MgSO
4+ normal hexane is selected as best purification combination.
3.3 matrix effect
Method of the present invention has been investigated the matrix effect (Fig. 4) of 7 kinds of mycotoxins in different substrates.Meanwhile, use Isotopic Internal Standard ([
13c
15]-DON) matrix effect is calibrated, found that the rear 3ADON of internal standard method calibration and 15ADON still exist serious matrix effect (approximately 40%) in pig feed and corn.Therefore, the corresponding calibration curve of matrix is used to the accurate quantitative analysis of mycotoxin in feed and grain sample.
3.4 linear relationships and detection limit, quantitative limit
With the standard operation solution of 7 kinds of mycotoxins of blank matrix (pig feed, chicken feed and corn) configuration.Concentration level is as shown in table 5.Under optimum experiment condition, investigate the range of linearity and detection limit (LOD), quantitative limit (LOD).Dependent linearity and LOD, LOQ value are in table 5
The linear relationship of 7 kinds of mycotoxins and detection limit, quantitative limit in table 5 different substrates
3.4, the recovery and Precision Experiment
Recovery test: (concentration of D3G and DOM is 400 μ g/kg, 200 μ g/kg, 20 μ g/kg to add the mixed mark of 7 kinds of mycotoxins of high, medium and low three levels in blank matrix; DON, NIV, 3ADON, 15ADON and FUSX concentration are 1000 μ g/kg, 500 μ g/kg, 50 μ g/kg).Process by 2.1 methods, each parallel 3 parts, add the recovery and the results are shown in Table 6.Withinday precision (RSDr) test: the mixed mark (adding concentration, same to recovery test) that adds 7 kinds of mycotoxins of high, medium and low three concentration levels in blank matrix.Within on the same day, according to 2.1 pre-treating methods, each level repeats 3 parts.Day to day precision (RSDR) test: the mixed mark (adding concentration the same) that adds respectively 7 kinds of mycotoxins of high, medium and low three concentration levels in blank matrix.In continuous 5 days, to process according to 2.1 methods, each level repeats 3 parts.
Precision concrete outcome is in table 6
The recovery of 7 kinds of mycotoxins and precision in table 6 different substrates
4, conclusion
The present invention uses improved dispersion solid phase extraction and liquid phase tandem mass spectrometry to measure the method for 7 kinds of mycotoxin levels in feed and cereal simultaneously.This method simple economy is reliable, sensitivity and stability high.It has solved the technical barrier of report method, for ensureing that China's feed safety provides good technical support.
Claims (6)
1. Liquid Chromatography-Tandem Mass Spectrometry method is measured a method for 7 kinds of mycotoxins in feed and cereal, it is characterized in that the method comprises the steps:
(1) take and pulverize rear feed or grain sample, add extraction solution, vortex and sonic oscillation are centrifugal after extracting, and get supernatant to be clean;
(2) supernatant is transferred in the centrifuge tube that contains anhydrous magnesium sulfate and degreasing solvent, after vortex vibration, removes normal hexane layer; Surplus solution nitrogen dries up rear constant volume;
(3) sample after constant volume carries out the qualitative and quantitative analysis of 7 kinds of mycotoxins by Liquid Chromatography-Tandem Mass Spectrometry instrument.
2. a kind of Liquid Chromatography-Tandem Mass Spectrometry method is measured the method for 7 kinds of mycotoxins in feed and cereal as claimed in claim 1, it is characterized in that in described step (1) that feed and cereal sample are: pig feed, chicken feed and corn.
3. Liquid Chromatography-Tandem Mass Spectrometry method is measured the method for 7 kinds of mycotoxins in feed and cereal as claimed in claim 1, it is characterized in that the extraction solution in described step (1) is 84% acetonitrile-aqueous solution, and methanol-water solution.
4. a kind of Liquid Chromatography-Tandem Mass Spectrometry method is measured the method for 7 kinds of mycotoxins in feed and cereal as claimed in claim 1, it is characterized in that the middle degreasing agent of described step (2) is for comprising normal hexane, sherwood oil, and other can remove the organic solvent of lipid material.
5. a kind of Liquid Chromatography-Tandem Mass Spectrometry method is measured the method for 7 kinds of mycotoxins in feed and cereal as claimed in claim 1, it is characterized in that in described step (3), the mycotoxin of surveying comprises: deoxynivalenol (DON), nivalenol (NIV), 3-acetyl group deoxynivalenol (3ADON), 15-acetyl group deoxynivalenol (15ADON) and fusarenon-X (FUSX), deoxynivalenol-3-glucoside (D3G) and decylization oxygen-deoxynivalenol (DOM).
6. a kind of Liquid Chromatography-Tandem Mass Spectrometry method is measured the method for 7 kinds of mycotoxins in feed and cereal as claimed in claim 1, it is characterized in that in described step (3) in liquid phase tandem mass spectrum that chromatographic column is for including but not limited to C
18, C
8chromatographic column, mobile phase includes but not limited to methyl alcohol, acetonitrile or aqueous solution.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237543A (en) * | 2015-11-19 | 2016-01-13 | 上海市农业科学院 | Method for purification preparation of N-sulfocarbamoyl toxins |
| CN106153784A (en) * | 2016-09-28 | 2016-11-23 | 山东出入境检验检疫局检验检疫技术中心 | Deoxynivalenol and the immunity affine purification high-efficiency liquid chromatography method for detecting of nivalenol in rice |
| CN107632093A (en) * | 2017-09-18 | 2018-01-26 | 河南工业大学 | A kind of ultrasonic degradation method of mycotoxin |
| 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 |
| CN108593832A (en) * | 2018-05-14 | 2018-09-28 | 广东省农业科学院农产品公共监测中心 | LC-MS-MS methods that are a kind of while measuring six kinds of mycotoxins in corn |
| CN109142584A (en) * | 2018-09-29 | 2019-01-04 | 广东省湛江市质量计量监督检测所 | A kind of method of mycotoxin in measurement shrimp feed |
| CN110007043A (en) * | 2019-04-25 | 2019-07-12 | 江苏省农业科学院 | The detection method of 9 kinds of mycotoxins in cereal |
-
2014
- 2014-04-10 CN CN201410152909.9A patent/CN103969364A/en active Pending
Non-Patent Citations (3)
| Title |
|---|
| AURELIEN DESMARCHELIER ET AL.: "Development and Comparison of Two Multiresidue Methods for the Analysis of 17 Mycotoxins in Cereals by Liquid Chromatography Electrospray Ionization Tandem Mass Spectrometry", 《J. AGRIC. FOOD CHEM.》 * |
| MICHAEL SULYOK ET AL.: "Development and validation of a liquid chromatography/tandem mass spectrometric method for the determination of 39 mycotoxins in wheat and maize", 《RAPID COMMUN. MASS SPECTROM.》 * |
| 武爱波 等: "中国与欧洲禾谷镰刀菌DON毒素HPLC定量比较分析", 《应用与环境生物学报》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237543A (en) * | 2015-11-19 | 2016-01-13 | 上海市农业科学院 | Method for purification preparation of N-sulfocarbamoyl toxins |
| CN106153784A (en) * | 2016-09-28 | 2016-11-23 | 山东出入境检验检疫局检验检疫技术中心 | Deoxynivalenol and the immunity affine purification high-efficiency liquid chromatography method for detecting of nivalenol in rice |
| CN107632093A (en) * | 2017-09-18 | 2018-01-26 | 河南工业大学 | A kind of ultrasonic degradation method of mycotoxin |
| 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 |
| CN108593832A (en) * | 2018-05-14 | 2018-09-28 | 广东省农业科学院农产品公共监测中心 | LC-MS-MS methods that are a kind of while measuring six kinds of mycotoxins in corn |
| CN109142584A (en) * | 2018-09-29 | 2019-01-04 | 广东省湛江市质量计量监督检测所 | A kind of method of mycotoxin in measurement shrimp feed |
| CN110007043A (en) * | 2019-04-25 | 2019-07-12 | 江苏省农业科学院 | The detection method of 9 kinds of mycotoxins in cereal |
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Application publication date: 20140806 |