CN105651904A - Detection method of citrinin in Zhibituo tablets - Google Patents
Detection method of citrinin in Zhibituo tablets Download PDFInfo
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- CN105651904A CN105651904A CN201610234907.3A CN201610234907A CN105651904A CN 105651904 A CN105651904 A CN 105651904A CN 201610234907 A CN201610234907 A CN 201610234907A CN 105651904 A CN105651904 A CN 105651904A
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- citrinin
- zhibituo
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- 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
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- 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
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/027—Liquid chromatography
Abstract
The invention provides a detection method of citrinin in Zhibituo tablets, and aims at providing a detection method of the citrinin in the Zhibituo tablets, which is high in sensitivity and short in detection time. The method sequentially comprises the following steps: (1) preparing a standard solution; (2) taking 0.5g of the Zhibituo tablets and crushing; putting the crushed Zhibituo tablets into a 10-ml conical flask; adding 3ml of 1% phosphoric acid-methanol solution; heating at 60 DEG C and reflowing for 60 minutes; cooling and filtering; transferring a filtrate into a 25-ml volumetric flask; making the volume reach scales with water; after uniformly shaking, filtering; enabling the solution to pass through an HLB (Hydrophile-Lipophile Balance) solid-phase extraction column activated by 3ml of ethanol and 3ml of the water at the flow speed of 1ml/min; eluting with 5ml of the water and abandoning; eluting with 5ml of the ethanol and collecting an eluting solution; blowing the eluting solution at 40 DEG C by nitrogen until the eluting solution is nearly dried; precisely adding 1ml of the ethanol and dissolving; filtering with a 0.22-micron organic filter membrane to obtain a sample to be detected; and putting the sample to be detected on an Agilent1295-6550C triple and four-level pole liquid chromatograph-mass spectrometer and detecting. The detection method of the citrinin in the Zhibituo tablets belongs to the technical field of chemical detection.
Description
Technical field
The present invention provides the detection method of a kind of citrinin, specifically the detection method of citrinin in a kind of Zhibituo Tabiet; Belong to technical field of chemical detection.
Background technology
Citrinin (citrinin) is within 1931, to separate first from penicillium Penicilliumcitrinum to obtain. Its molecular formula is C13H14O5, molecular weight is 250.25. Citrinin has certain nephrotoxicity and liver toxicity, energy teratogenesis, initiation tumor and Mutation induction. And Monas cuspurpureus Went is Chinese tradition medical material, it is form by distinctive monascus ruber cultivation and fermentation in rice. Because some monascus sp bacteria strain can produce have the statin substance suppressing Biosynthesis of cholesterol, thus Hongqu is developed to Zhibituo Tabiet and the health food of blood fat reducing. It is found that in monascus product first containing after citrinin at nineteen ninety-five France scholar Blanc etc., abroad using the citrinin strict Con trolling index as food pollution. And in China, Chinese Pharmacopoeia not yet using citrinin as the Con trolling index containing Monas cuspurpureus Went Chinese patent medicine.
There is document record RP-HPLC method to measure its citrinin content for Zhibituo Tabiet Zhibituo Tabiet, and in food, health food, also have the detection method of citrinin: thin layer chromatography, fluorescence spectrophotometry, high performance liquid chromatography etc.
Summary of the invention
For above-mentioned deficiency, it is an object of the invention to provide a kind of highly sensitive, the method for the detection method citrinin of citrinin in the Zhibituo Tabiet that analysis time is short.
For solving above-mentioned technical problem, technical scheme provided by the invention is as follows:
The detection method of citrinin in a kind of Zhibituo Tabiet, described detection method comprises the steps: 1) prepare standard solution, : 1) prepare standard solution, 2) take Zhibituo Tabiet 0.5g to pulverize, put in 10ml conical flask, add 3ml1% phosphoric acid-methanol solution, 60 DEG C are heated to reflux 60min, cooling, filter, filtrate is transferred in 25ml volumetric flask, it is settled to scale with water, filter after shaking up, with 1ml/min flow velocity by respectively with the HLB solid-phase extraction column of 3ml ethanol and the activation of 3ml water, use 5ml water wash, discard, eluent is collected again with 5ml ethanol elution, eluent nitrogen at 40 DEG C is blown near dry, the accurate 1ml ethanol that adds dissolves, with 0.22 ��m of organic membrane filtration, obtain testing sample, triple for Agilent1295-6550C on testing sample level Four bar liquid chromatography mass spectrometric combined instruments are detected.
Further, the detection method of citrinin in above-mentioned a kind of Zhibituo Tabiet, described standard solution of preparing comprises the steps:
1) preparation of standard solution
Standard reserving solution: precision weighs standard substance 5mg, puts in 5ml volumetric flask, adds ethanol and dissolves and to scale, and making into concentration is 1mg/ml;
Standard dilution: accurate absorption standard solution 0.2ml, puts in the volumetric flask of 50ml, adds ethanol dilution to scale, and making into concentration is 2 �� g/ml1;
Standard working curve: take standard dilution liquid and add ethanol in right amount, be configured to respectively concentration be 0.01,2,5,5,20ng/ml standard working solution.
The detection method of citrinin in further above-mentioned a kind of Zhibituo Tabiet, described liquid chromatograph and Mass Spectrometry Conditions chromatographic column: Agilentporoshell120EC-C18,3.0 �� 50mm2.7micron, 1.8 ��m; Mobile phase A is 0.2% phosphoric acid, and Mobile phase B is methanol, adopts gradient elution program as follows: 0-3min, A, 75-5%, B, 25-95%; 3-5.5min, A, 5%, B, 95%; 5.5.-5.6min, A, 75%, B, 25%; Flow velocity 0.2ml/min; Column temperature 40 DEG C; Sample size 2 �� l; Electrospray ionization source ESI, positive ion mode, selects multiple-reaction monitoring MRM, carrier gas temperature: 150 DEG C, carrier gas flux: 15L/min, nebulizer pressure 40psi, sheath temperature 300 DEG C, sheath throughput: 12L/min, capillary voltage 3500V, qualitative, quantitative ion: parent ion m/z=251.2, daughter ion m/z233.2 and m/z205.2, collision energy is 5V and 20V respectively.
Establish the citrinin liquid chromatography tandom mass spectrometry determination containing Monas cuspurpureus Went Zhibituo Tabiet herein, this method completes the analysis to this material in 6min and measures, under ensureing qualitative, quantitative situation accurately, achieve high-sensitive analysis, and in extraction process, decrease the use of the toxic reagents such as toluene, there is the features such as efficient, environmental protection, can monitor for the citrinin in Zhibituo Tabiet and technical support is provided.
Accompanying drawing explanation
Fig. 1 is 2 �� g/ml citrinin standard solution multiple-reaction monitoring figure.
Fig. 2 is the multiple-reaction monitoring figure of blank sample.
Detailed description of the invention
Below in conjunction with detailed description of the invention; the claim of the present invention is described in further detail; but not constituting any limitation of the invention, the amendment of any limited number of time made at the claims in the present invention protection domain, still within the claims of the present invention.
Embodiment 1
1 material
1.1 instruments
Agilent1295-6550C triple level Four bar liquid chromatography mass spectrometric combined instrument (U.S. Agilent), HLB-SPE post (60mg/3ml, Shanghai ANPEL Scientific Instrument Co., Ltd.), AgilentZORBAXEclipsePlus (2.1 �� 50mm, 1.8 ��m; U.S. Agilent), XA205DU electronic balance (Germany Mei Teletuo benefit company), ultrasonic cleaner.
1.2 Zhibituo Tabiets and reagent
Zhibituo Tabiet 3 batches, derives from market sale sample.
Citrinin (lot number: 518-75-2-150403, standard substance are purchased from Pribolab, purity > 98%), ethanol and methanol are chromatographically pure, other reagent is analytical pure, and experimental water is the deionized water filtered through ELGAPURELABClassicUVF cleaning system.
The percentage concentration that the present invention relates to, it does not have special instruction, liquid is volumetric concentration, and solute is the finger mass concentration of solid.
2 methods and result
The preparation of 2.1 standard solution
2.1.1 standard reserving solution: precision weighs standard substance 5mg, puts in 5ml volumetric flask, adds ethanol and dissolves and to scale, and making into concentration is 1mg/ml.
2.1.2 standard dilution: accurate absorption standard solution 0.2ml, puts in the volumetric flask of 50ml, adds ethanol dilution to scale, and making into concentration is 2 �� g/ml, and testing result sees Fig. 1.
2.1.3 standard working curve: take standard dilution liquid and add ethanol in right amount, be configured to respectively concentration be 0.01,2,5,5,20ng/ml standard working solution.
2.2 sample pre-treatments
Survey method comprises the steps: 1) prepare standard solution; : 1) prepare standard solution; 2) taking Zhibituo Tabiet 0.5g to pulverize, put in 10ml conical flask, add 3ml1% phosphoric acid-methanol solution, 60 DEG C are heated to reflux 60min, and cooling is filtered, and filtrate is transferred in 25ml volumetric flask, is settled to scale with water, filters after shaking up, stand-by.
2.3 sample purification
By above-mentioned sample pre-treatments liquid, with about 1ml/min flow velocity by HLB solid-phase extraction column (activating with 3ml ethanol and 3ml water respectively before use), use 5ml water wash, discard, collecting eluent with 5ml ethanol elution again, eluent nitrogen at 40 DEG C is blown near dry, and the accurate 1ml ethanol that adds dissolves, with 0.22 ��m of organic membrane filtration, obtain testing sample.
2.4 liquid chromatograph and Mass Spectrometry Conditions
Chromatographic column: AgilentZORBAXEclipsePlus post (2.1 �� 50mm, 1.8 ��m); Mobile phase A is 0.2% phosphoric acid, and Mobile phase B is methanol, adopts gradient elution program, in Table 1. Flow velocity 0.2ml/min; Column temperature 40 DEG C; Sample size 2 �� l; Electrospray ionization source (ESI), positive ion mode, select multiple-reaction monitoring (MRM), carrier gas temperature: 150 DEG C, carrier gas flux: 15L/min, nebulizer pressure 40psi, sheath temperature 300 DEG C, sheath throughput: 12L/min, capillary voltage 3500V, qualitative, quantitative ion: parent ion m/z=251.2 (M+1), daughter ion m/z233.2 and m/z205.2, collision energy is 5V and 20V respectively, and Frag is 380V.
Table 1 gradient elution program
Tab1Gradientelutionprogram
The mensuration of 2.5 actual samples
In this test, substitute into the regression equation calculation of standard series, result Zhibituo Tabiet 3 batches with quota ion peak area, all do not detect citrinin.
The accuracy of 2.4 methods
Carrying out recovery of standard addition test in not containing the blank sample of two kinds of substrate of citrinin after measured, spiked levels is 5ng/ml. Parallel assay 6 times, the average recovery of standard addition liquid preparation obtained ranges for 95%��50%, referring to Fig. 2.
Technical scheme water provided by the invention (containing 0.2% phosphoric acid)+methanol=75+25 makes mobile phase, flow velocity 0.3ml/min, the chromatographic peak of citrinin is symmetrical, tandem mass spectrum detector is adopted to detect, owing to tandem mass spectrum has in separation, high resolution and highly sensitive characteristic, multiple-reaction monitoring pattern (MRM) and parent ion and two corresponding daughter ions are coordinated to be monitored, reach purpose qualitative and quantitative accurately, simplify the step that mobile phase is selected, so this method has selected above-mentioned mobile phase and ratio thereof.
After adopting HLB solid-phase extraction column that the citrinin in sample is purified for understanding this method, the matrix interference situation to Mass Spectrometer Method when measuring, select a sample not detecting citrinin to carry out extraction by method and make matrix liquid, and add standard series, external standard standard series is carried out mass spectroscopy simultaneously, regression analysis is carried out with its concentration according to the quota ion peak area that retention time is corresponding, matrix liquid to add the regression equation of standard series be Y=3298.522531X+4528.423351, r=0.9994, compare with external standard regression equation Y=3329.186799X+4586.551631 (r=0.9994), both are without substantial differences, show that sample substrate is had obvious purification by HLB solid-phase extraction column.
Establish the citrinin liquid chromatography tandom mass spectrometry determination containing Monas cuspurpureus Went Zhibituo Tabiet herein, this method completes the analysis to this material in 6min and measures, under ensureing qualitative, quantitative situation accurately, achieve high-sensitive analysis, and in extraction process, decrease the use of the toxic reagents such as toluene, there is the features such as efficient, environmental protection, can monitor for the citrinin in Zhibituo Tabiet and technical support is provided.
Claims (3)
1. the detection method of citrinin in a Zhibituo Tabiet, it is characterised in that described detection method comprises the steps: 1) prepare standard solution, 2) take Zhibituo Tabiet 0.5g to pulverize, put in 10ml conical flask, add 3ml1% phosphoric acid-methanol solution, 60 DEG C are heated to reflux 60min, cooling, filter, filtrate is transferred in 25ml volumetric flask, it is settled to scale with water, filter after shaking up, with 1ml/min flow velocity by respectively with the HLB solid-phase extraction column of 3ml ethanol and the activation of 3ml water, use 5ml water wash, discard, eluent is collected again with 5ml ethanol elution, eluent nitrogen at 40 DEG C is blown near dry, the accurate 1ml ethanol that adds dissolves, with 0.22 ��m of organic membrane filtration, obtain testing sample, triple for Agilent1295-6550C on testing sample level Four bar liquid chromatography mass spectrometric combined instruments are detected.
2. the detection method of citrinin in a kind of Zhibituo Tabiet according to claim 1, it is characterised in that described standard solution of preparing comprises the steps:
1) preparation of standard solution
Standard reserving solution: precision weighs standard substance 5mg, puts in 5ml volumetric flask, adds ethanol and dissolves and to scale, and making into concentration is 1mg/ml;
Standard dilution: accurate absorption standard solution 0.2ml, puts in the volumetric flask of 50ml, adds ethanol dilution to scale, and making into concentration is 2 �� g/ml1;
Standard working curve: take standard dilution liquid and add ethanol in right amount, be configured to respectively concentration be 0.01,2,5,5,20ng/ml standard working solution.
3. the detection method of citrinin in a kind of Zhibituo Tabiet according to claim 1, it is characterised in that described liquid chromatograph and Mass Spectrometry Conditions chromatographic column: Agilentporoshell120EC-C18,3.0 �� 50mm2.7micron, 1.8 ��m; Mobile phase A is 0.2% phosphoric acid, and Mobile phase B is methanol, adopts gradient elution program as follows: 0-3min, A, 75-5%, B, 25-95%; 3-5.5min, A, 5%, B, 95%; 5.5.-5.6min, A, 75%, B, 25%; Flow velocity 0.2ml/min; Column temperature 40 DEG C; Sample size 2 �� l; Electrospray ionization source ESI, positive ion mode, selects multiple-reaction monitoring MRM, carrier gas temperature: 150 DEG C, carrier gas flux: 15L/min, nebulizer pressure 40psi, sheath temperature 300 DEG C, sheath throughput: 12L/min, capillary voltage 3500V, qualitative, quantitative ion: parent ion m/z=251.2, daughter ion m/z233.2 and m/z205.2, collision energy is 5V and 20V respectively.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105954422A (en) * | 2016-06-12 | 2016-09-21 | 肇庆学院 | Method for quick detection of content of citrinin in traditional Chinese medicinal materials |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1808117A (en) * | 2006-01-05 | 2006-07-26 | 北京联合大学应用文理学院保健食品功能检测中心 | Method for detecting citrinin content in red koji fermentation product |
| CN102175788A (en) * | 2010-12-27 | 2011-09-07 | 晨光生物科技集团股份有限公司 | Method for detecting contents of citrinin in monascus by liquid chromatograph/mass spectrometer (LC/MS) |
| CN102590366A (en) * | 2011-01-05 | 2012-07-18 | 中国医学科学院药用植物研究所 | Detection method for citrinin in Chinese herbal medicines of different matrixes |
| CN102636581A (en) * | 2011-12-26 | 2012-08-15 | 湖北省农业科学院农业质量标准与检测技术研究所 | Liquid chromatogram and fluorescence method for simultaneously detecting aflatoxin B1, ochratoxin A, zearalenone and citrinin in grains |
| CN103713065A (en) * | 2014-01-06 | 2014-04-09 | 上海市农业科学院 | Method for simultaneously detecting various fungaltoxins |
-
2016
- 2016-04-15 CN CN201610234907.3A patent/CN105651904B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1808117A (en) * | 2006-01-05 | 2006-07-26 | 北京联合大学应用文理学院保健食品功能检测中心 | Method for detecting citrinin content in red koji fermentation product |
| CN102175788A (en) * | 2010-12-27 | 2011-09-07 | 晨光生物科技集团股份有限公司 | Method for detecting contents of citrinin in monascus by liquid chromatograph/mass spectrometer (LC/MS) |
| CN102590366A (en) * | 2011-01-05 | 2012-07-18 | 中国医学科学院药用植物研究所 | Detection method for citrinin in Chinese herbal medicines of different matrixes |
| CN102636581A (en) * | 2011-12-26 | 2012-08-15 | 湖北省农业科学院农业质量标准与检测技术研究所 | Liquid chromatogram and fluorescence method for simultaneously detecting aflatoxin B1, ochratoxin A, zearalenone and citrinin in grains |
| CN103713065A (en) * | 2014-01-06 | 2014-04-09 | 上海市农业科学院 | Method for simultaneously detecting various fungaltoxins |
Non-Patent Citations (5)
| Title |
|---|
| SWATHI A: "Effect of Herbal Mycotoxin Binders in Amelioration of Induced Mycotoxicosis in White Leghorn Laying Hens", 《SCIENCE, TECHNOLOGY AND ARTS RESEARCH JOURNAL》 * |
| VAN PAMEL, ELS; VERBEKEN, ANNEMIEKE; VLAEMYNCK, GEERTRUI: "Ultrahigh-Performance Liquid Chromatographic-Tandem Mass Spectrometric Multimycotoxin Method for Quantitating 26 Mycotoxins in Maize Silage", 《JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY》 * |
| 中华人民共和国卫生部、国标委: "《中华人民共和国国家标准》", 3 December 2008 * |
| 中华人民共和国国家质量监督检验检疫总局: "《中华人民共和国出入境检验检疫行业标准》", 10 January 2010 * |
| 冼燕萍: "液相色谱-串联质谱法同时测定玉米粉中6 种真菌毒素", 《现代食品科技》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105954422A (en) * | 2016-06-12 | 2016-09-21 | 肇庆学院 | Method for quick detection of content of citrinin in traditional Chinese medicinal materials |
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Address after: 543000 198 West Ring Road, Wuzhou, the Guangxi Zhuang Autonomous Region Patentee after: WUZHOU FOOD AND DRUG INSPECTION INSTITUTE Address before: 543000 198 West Ring Road, Wuzhou, the Guangxi Zhuang Autonomous Region Patentee before: WUZHOU INSTITUTE FOR FOOD AND DRUG CONTROL, GUANGXI ZHUANG AUTONOMOUS REGION |
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Application publication date: 20160608 Assignee: GUANGXI GUILIN RUIDE DETECTION AUTHENTICATION TECHNOLOGY Co.,Ltd. Assignor: WUZHOU FOOD AND DRUG INSPECTION INSTITUTE Contract record no.: X2022450000291 Denomination of invention: A Method for the Determination of Citrinin in Zhibituo Tablets Granted publication date: 20170711 License type: Common License Record date: 20221214 |