CN102608245A - Method for rapidly detecting prohibited additive acid orange in red flower by liquid chromatography-mass spectrometry - Google Patents
Method for rapidly detecting prohibited additive acid orange in red flower by liquid chromatography-mass spectrometry Download PDFInfo
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Abstract
The invention discloses a method for rapidly detecting a prohibited additive acid orange in a red flower by liquid chromatography-mass spectrometry, which utilizes a super-efficient liquid chromatography-tandem mass spectrometry technology and takes ammonium acetate solution-acetonitrile as a fluid phase, wherein the concentration of the ammonium acetate solution is 0.01 mol/mL; the fluid phase is separated by a C18 chromatographic column; a secondary ion fragment is quantitatively detected by electrically spraying an ion source and combining with an ionized characteristic of a detected component under the condition of utilizing secondary mass spectrographic analysis of a negative ion mode, so as to more accurately detect the content of the prohibited additive acid orange in the red flower. The method disclosed by the invention is strong in specificity and can be simultaneously qualitative and quantitative; the pre-treatment is simple and fast and has a fast analyzing speed; the interference of similar compounds can be eliminated, the detected component is ensured to be accurate and reliable; the detection flexibility is high and the repeatability is good; and therefore, the method is suitable for rapidly and quantitatively sieving and evaluating the prohibited additive acid orange in the red flower by a drug detection mechanism.
Description
Technical field
The invention belongs to and adopt Modern Analytical Instrument to detect the additive technical field of violating a ban in the safflower, relate to the detection method of golden yellow powder, a kind of method that is applicable to the golden yellow powder of additive of violating a ban in drug testing institution's rapid screening safflower of saying so more specifically.
Background technology
The golden yellow powder of seed is a kind of abiotic synthetic coloring matter, is one of important fine chemical product.Golden yellow powder has another name called Acid Orange II, acid golden yellow II, gold orange II or acid gorgeous orange GR, chemistry beta naphthal azo P-TOLUENE SULFO ACID 99 sodium by name, molecular formula: C
16H
11N
2NaO
4S, relative molecular mass: 350.33, be soluble in ethanol, acetonitrile etc.Golden yellow powder is mainly used in the dyeing of silk, knitting wool and wool, the direct printing of wool, silk and nylon fabric, leather and paper painted etc.; In addition, it is again a kind of indicator, medically is usually used in the dyeing of histotomy.Structural formula is following:
Golden yellow powder belongs to non-food coloring, has stronger toxicity and carcinogenicity, and relevant regulations are all forbidden golden yellow powder is used for food color both at home and abroad.Golden yellow powder does not fade than common food coloring is more easy to change, and lovely luster, good penetrability, cheap, have certain fastness.Generally speaking, azo dyes itself can not produce deleterious effect to human body, but water miscible azo dyes can be resolved into aromatic amine by intestinal; Non-water-soluble azo dyes then can be absorbed by liver, is become aromatic amine by the enzyme decomposition-reduction in the liver, and some aromatic amine is mutagen or carcinogen; Or other biological toxicity arranged; These compounds are absorbed by human body once more, through activation, can make the change of human body cell recurring structure and function; Be transformed into the human lesion risk factor, thereby increase carcinogenic possibility.In state compulsory standard, be " must not detect " to the check term of violated pigments such as golden yellow powder.
At present the method for inspection for non-edible golden yellow powder also has, and analyses and oscilloscopic polarography etc. like liquid phase chromatography, ply of paper.Xiao Baiman etc. have set up the method for golden yellow powder in the high-performance liquid chromatogram determination food, measure when being applicable to golden yellow powder of non-food coloring and synthetic food colors.Chen Dayi etc. have proposed to analyse with ply of paper qualitative, the method for golden yellow powder in the oscillographic polarography quantitative measurement part food, and detected the golden yellow powder that adds in commercially available chilli powder, the spiced and stewed food with this method.Utilization fluorescence spectrum technology for detection such as Liu Zhou Yi contain the WS of golden yellow powder; Think that golden yellow powder can produce fluorescence; Be because phenyl ring and the naphthalene ring absorbing ultraviolet light energy that contains in its molecule; And azo bond is behind the excited singlet that forms cis-isomer under the photon effect, due to the photon of both emissions.These results to golden yellow powder the violated use in food detect, the more further investigation of characteristic present and molecule rule, certain reference value is arranged.
Safflower is the tubular corolla of feverfew safflower Carthamus tinctorius L., is a kind of rare traditional Chinese medicine, the activating blood to promote menstruation that tool is good, the effect of blood stasis removing analgesic.Because the source of goods is more scarce in recent years, rise in price, the lawless person often mixes other material and dyeing is played tricks.Through identifying that its dyeing is a kind of chemical dyestuff Acid Orange II (having another name called golden yellow powder), these article have suspicious carcinogenesis, forbid in food, using; The detection of present golden yellow powder is still blank and has only several pieces of documents seldom in national standard and industry standard; Also be liquid phase process generally, do not have the relevant method research of mass spectrum, we grope through a large amount of experiments; Set up the method for golden yellow powder in the LC-MS method fast detecting safflower; This method is sensitive high, simple and easy to do, has obtained satisfied effect, is applicable to the mensuration of golden yellow powder in the safflower.
Summary of the invention
The objective of the invention is to set up the method for the violated golden yellow powder of additive in the LC-MS method fast detecting safflower, promptly carry out rapid screening, can measure its content exactly simultaneously whether containing golden yellow powder in the safflower.
The invention provides that a kind of pre-treating method is simple and efficient, the method for the golden yellow powder of additive of violating a ban in the fast detecting safflower that shortens analysis time and low detectability, be applicable to fast quantification examination and the evaluation of the drug testing institution to the golden yellow powder of additive of violating a ban in the safflower.
The present invention realizes through following technical scheme:
Violate a ban in the LC-MS method fast detecting safflower method of the golden yellow powder of additive comprises that mainly sample preparation, chromatographic resolution and three aspects of Mass Spectrometer Method is characterized in that this method carries out as follows:
(1) preparation of need testing solution: get and pulverize the also about 1g of sample of mixing, the accurate title, decide, and puts in the tool plug conical flask, accurate adding 0.01mol/mL ammonium acetate solution-acetonitrile (70:30) 25mL; Close plug is claimed to decide weight, and ultrasonic Extraction 30 minutes is put cold; Claim again to decide weight, and supply the weight that subtracts mistake, shake up; Filter, get subsequent filtrate, subsequent use;
(2) preparation of reference substance solution: it is an amount of that precision takes by weighing golden yellow powder reference substance, adds methyl alcohol and process the solution that every 1mL contains golden yellow powder reference substance 0.16 μ g respectively, subsequent use;
(3) determination method by liquid chromatography-electrospray mass:
Chromatographic condition: adopt C
18Liquid-phase chromatographic column: Waters BEH C
18(2.1mm * 50mm, 1.7mm); With 0.01mol/mL ammonium acetate solution-acetonitrile (70:30) is moving phase; Flow velocity 0.2mL/min; Column temperature is 30 ℃; Sample size 10 μ L.
The mass spectrum condition: adopt electric spray ion source, negative ion electrospray leaves pattern, kapillary ionization voltage 2.5kv, sampling taper hole voltage 15v; 110 ℃ of ion source temperatures, 300 ℃ of desolventizing temperature, desolventizing nitrogen flow rate 550L/hr, taper hole blowback nitrogen 50L/hr; Scan pattern is multiple-reaction monitoring MRM, acquisition time 0～5min, sweep time 0.3s; Interval time, 0.02s selected ion m/z327Da as object ion, collision voltage 30v; Qualitative ion is m/z93Da, m/z171Da and m/z247Da, and quota ion is m/z156Da, can lock the content of golden yellow powder in the sample accurately through quota ion.
(4) quantitative measurement of golden yellow powder: the same step of instrumental method (3); Reference substance solution and need testing solution be sample introduction 10 μ L respectively; Extracting quota ion at reference substance mass spectrogram and sample mass spectrum chromatogram is that the chromatogram of m/z156Da carries out integration, measures the peak area of golden yellow opaque spectrum chromatographic peak.
(5) according to the integration peak area of golden yellow powder in the standard items and the data of concentration, the content of golden yellow powder in the calculation sample.
(6) above-mentioned definite assay method is carried out efficiency evaluation, comprising specificity, linearity, precision, repeatability, stability, measurement range.
Method for quick of the present invention is preferably got and has been pulverized the also about 1g of sample of mixing, and accurate the title decides, and puts in the tool plug conical flask; Accurate 0.01mol/L ammonium acetate solution-acetonitrile (volume ratio 70:30) 25mL that adds, close plug claims to decide weight, ultrasonic Extraction 30 minutes; Put coldly, claim again to decide weight, and supply the weight that subtracts mistake; Shake up, filter, get subsequent filtrate.
Method for quick of the present invention, wherein the relative retention time of golden yellow powder is at 5min, reaches well with the sample mesostroma and separates.
Method for quick of the present invention under collision voltage 30v, extracts the second order ms figure of quasi-molecular ions m/z156Da; Wherein the characteristic fragment ion peak group of golden yellow powder is m/z93Da, m/z171Da and m/z247Da.
Method for quick of the present invention, but the identical or close Chinese patent drug that contains the flos carthami of golden yellow powder and contain safflower of the detection method Detection and Extraction method of golden yellow powder wherein.
Method for quick of the present invention, preferred 0.01mol/L ammonium acetate solution-acetonitrile (volume ratio 70:30) adopts ultrasonic extracting method, sonicated 30min as extracting solvent.Good to the target component extraction effect, and method is simple to operation, experimental result, and the recovery of this method, repeatability and extraction efficiency all reach requirement.
One of gordian technique of the present invention is through the fast detecting of LC-MS method with golden yellow powder, preferred assay method: chromatographic condition: adopt C
18Liquid-phase chromatographic column: Waters BEH C
18(2.1mm * 50mm, 1.7mm); With 0.01mol/mL ammonium acetate solution-acetonitrile (70:30) is moving phase, can realize that golden yellow powder is with the quick separation of matrix in 5 minutes.
The mass spectrum condition: adopt electric spray ion source, negative ion electrospray leaves pattern, kapillary ionization voltage 2.5kv, sampling taper hole voltage 15v; 110 ℃ of ion source temperatures, 300 ℃ of desolventizing temperature, desolventizing nitrogen flow rate 550L/hr, taper hole blowback nitrogen 50L/hr; Scan pattern is multiple-reaction monitoring MRM, acquisition time 0～5min, sweep time 0.3s; Interval time, 0.02s selected ion m/z327Da as object ion, collision voltage 30v; Qualitative ion is m/z93Da, m/z171Da and m/z247Da, and quota ion is m/z156Da, can lock the content of golden yellow powder in the sample accurately through quota ion.
The present invention shows through methodological study; Handle sample with 0.01mol/L ammonium acetate solution-acetonitrile (volume ratio 70:30) as extracting solvent supersonic; Adopt the content of the golden yellow powder in the LC-MS method fast detecting sample, detect and be limited to 0.8ng, quantitative limit 2.4ng; The recovery reach 96.28% (RSD=1.8, n=6); The range of linearity be 2.4ng-240ng (linear equation y=8.6205x+2.3468, r=0.9996); The measured deviation of measuring golden yellow powder content in the safflower is 0.06-1.32%.
The present invention compares the good effect that is had with existing detection technique and is:
(1) the present invention's content of golden yellow powder in the public use LC-MS method fast measuring safflower first can be accomplished detection in the 5min.
(2) method for quick of the present invention, its advantage is simple and easy to do, the method strong operability, the recovery is high, favorable reproducibility.
(3) the present invention adopts second order ms, is that the content to golden yellow powder carries out accurate qualitative-and-quantitative method on the mass spectrum aspect.
Description of drawings
Fig. 1, golden yellow powder standard items total ion current TIC collection of illustrative plates;
Fig. 2, the qualitative ion of golden yellow powder standard items (m/z93Da, m/z171Da and m/z247Da) collection of illustrative plates;
Fig. 3, golden yellow powder standard items quota ion (m/z156Da) collection of illustrative plates;
Fig. 4, safflower sample total ion current TIC collection of illustrative plates;
Fig. 5, the qualitative ion of safflower sample (m/z93Da, m/z171Da and m/z247Da) collection of illustrative plates;
Fig. 6, safflower sample quota ion (m/z156Da) collection of illustrative plates.
Embodiment
Below in conjunction with embodiment the present invention is described; The scheme of embodiment described here; Do not limit the present invention; One of skill in the art can make improvements and change according to spirit of the present invention, and described these improvement and variation all should be regarded as within the scope of the invention, and scope of the present invention and essence are limited claim.Wherein said all ingredients unless otherwise indicated, other all has commercially available.
Embodiment 1
1, instrument and material
The triple level Four bar of U.S. Waters Acquity UPLC/Waters Quattro Premier XE LC-MS appearance is equipped with electric spray ion source (ESI) and Masslynx4.1 data acquisition software.
2, medicine and reagent
Golden yellow powder orange II sodium salt (Dr.Ehrenstorfer GmbH company, lot number: 50513); Acetonitrile (chromatographically pure, U.S. fisher company), ammonium acetate (chromatographically pure, Tianjin recovery fine chemistry industry research institute, on June 19th, 2011), ultrapure water (the 0.22um filter membrane is crossed by milli Q ultrapure water system).
3, method
Get and pulverize the also about 1g of commercially available A producer's flos carthami of mixing, the accurate title, decide, and puts in the tool plug conical flask, accurate adding 0.01mol/L ammonium acetate solution-acetonitrile (volume ratio 70:30) 25mL; Close plug is claimed to decide weight, and ultrasonic Extraction 30 minutes is put cold; Claim again to decide weight, and supply the weight that subtracts mistake, shake up; Filter, get subsequent filtrate, subsequent use;
The preparation of reference substance solution: it is an amount of that precision takes by weighing golden yellow powder reference substance, adds methyl alcohol and process the solution that every 1mL contains golden yellow powder reference substance 0.24 μ g respectively, subsequent use;
Chromatographic condition: adopt C
18Liquid-phase chromatographic column: Waters BEH C
18(2.1mm * 50mm, 1.7mm); With 0.01mol/mL ammonium acetate solution-acetonitrile (70:30) is moving phase; Flow velocity 0.2mL/min; Column temperature is 30 ℃; Sample size 10 μ L.
The mass spectrum condition: adopt electric spray ion source, negative ion electrospray leaves pattern, kapillary ionization voltage 2.5kv, sampling taper hole voltage 15v; 110 ℃ of ion source temperatures, 300 ℃ of desolventizing temperature, desolventizing nitrogen flow rate 550L/hr, taper hole blowback nitrogen 50L/hr; Scan pattern is multiple-reaction monitoring MRM, acquisition time 0～5min, sweep time 0.3s; Interval time, 0.02s selected ion m/z327Da as object ion, collision voltage 30v; Qualitative ion is m/z93Da, m/z171Da and m/z247Da, and quota ion is m/z156Da, can lock the content of golden yellow powder in the sample accurately through quota ion.
The quantitative measurement of golden yellow powder: reference substance solution and need testing solution be sample introduction 10 μ L respectively, are that the mass spectrum chromatographic peak of m/z156Da carries out integration, the content of golden yellow powder in the calculation sample at reference substance mass spectrogram and sample mass spectrum chromatogram extraction quota ion.Testing result is seen table 1.
Golden yellow powder content is measured the result in the commercially available A of the table 1 producer safflower
Embodiment 2
Get and pulverize the also about 1g of commercially available B producer's flos carthami of mixing; Pre-treatment side and instrument condition are with reference to embodiment 1; Reference substance solution and need testing solution be sample introduction 10 μ L respectively; Extracting quota ion at reference substance mass spectrogram and sample mass spectrum chromatogram is that the chromatogram of m/z156Da carries out integration, measures the peak area of golden yellow opaque spectrum chromatographic peak; The content of golden yellow powder in the calculation sample.Testing result is seen table 2.
Golden yellow powder content is measured the result in the commercially available B of the table 2 producer safflower
Embodiment 3
Get and pulverize and the commercially available C producer of mixing contains the about 2g of Chinese patent drug of safflower; Pre-treatment side and instrument condition are with reference to embodiment 1; Reference substance solution and need testing solution be sample introduction 10 μ L respectively; Extracting quota ion at reference substance mass spectrogram and sample mass spectrum chromatogram is that the chromatogram of m/z156Da carries out integration, measures the peak area of golden yellow opaque spectrum chromatographic peak; The content of golden yellow powder in the calculation sample.Testing result is seen table 3.
The commercially available C of table 3 producer contains in the Chinese patent drug of safflower golden yellow powder content and measures the result
After the preferred embodiment that specifies; Being familiar with this technological personage can be well understood to; Do not break away from above-mentioned claim with spirit under can carry out various variations and modification; All foundations technical spirit of the present invention all belongs to the scope of technical scheme of the present invention to any simple modification, equivalent variations and modification that above embodiment did.And the embodiment that the present invention also is not subject in the instructions to be given an actual example.
Claims (7)
1. violate a ban in the LC-MS method fast detecting safflower method of the golden yellow powder of additive is characterized in that this method undertaken by following step:
(1) preparation of need testing solution: get and pulverize the also sample 1g of mixing, the accurate title, decide, and puts in the tool plug conical flask, accurate adding 0.01mol/L ammonium acetate solution-acetonitrile 25mL; Close plug is claimed to decide weight, and ultrasonic Extraction 30 minutes is put cold; Claim again to decide weight, and supply the weight that subtracts mistake, shake up; Filter, get subsequent filtrate, subsequent use;
(2) preparation of reference substance solution: it is an amount of that precision takes by weighing golden yellow powder reference substance, adds methyl alcohol and process the solution that every 1mL contains golden yellow powder reference substance 0.24 μ g respectively, subsequent use;
(3) determination method by liquid chromatography-electrospray mass:
Chromatographic condition: adopt C
18Liquid-phase chromatographic column: Waters BEH C
18(2.1mm * 50mm, 1.7mm); With 0.01mol/mL ammonium acetate solution-acetonitrile is moving phase; Flow velocity 0.2 mL/min; Column temperature is 30 ℃; Sample size 10 μ L;
The mass spectrum condition: adopt electric spray ion source, negative ion electrospray leaves pattern, kapillary ionization voltage 2.5kv, sampling taper hole voltage 15v; 110 ℃ of ion source temperatures, 300 ℃ of desolventizing temperature, desolventizing nitrogen flow rate 550L/hr, taper hole blowback nitrogen 50L/hr; Scan pattern is multiple-reaction monitoring MRM, acquisition time 0～5min, sweep time 0.3s; Interval time, 0.02s selected ion m/z327Da as object ion, collision voltage 30v; Qualitative ion is m/z93Da, m/z171Da and m/z247Da, and quota ion is m/z156Da, locks the content of golden yellow powder in the sample accurately through quota ion;
(4) quantitative measurement of golden yellow powder: the same step of instrumental method (3); Reference substance solution and need testing solution be sample introduction 10 μ L respectively; Extracting quota ion at reference substance mass spectrogram and sample mass spectrum chromatogram is that the chromatogram of m/z156Da carries out integration, measures the peak area of golden yellow opaque spectrum chromatographic peak;
(5) according to the integration peak area and the concentration data of golden yellow powder standard items, the content of golden yellow powder in the calculation sample.
2. the described method for quick of claim 1, wherein moving phase ammonium acetate solution in the step (1): the volume ratio of acetonitrile is 70:30.
3. the described method for quick of claim 1, wherein moving phase ammonium acetate solution in the step (3): the volume ratio of acetonitrile is 70:30.
4. the described method for quick of claim 1, wherein the relative retention time of golden yellow powder is at 5min, reaches well with the sample mesostroma and separates.
5. the described method for quick of claim 1 under collision voltage 30v, extracts the second order ms figure of quasi-molecular ions m/z156Da; Wherein the characteristic fragment ion peak group of golden yellow powder is m/z93Da, m/z171Da and m/z247Da.
6. claims 1～5 each said LC-MS detects method application aspect the golden yellow powder of interpolation in preparation detection medicine of golden yellow powder.
7. claims 1～5 each described method for quick, but the identical or close Chinese patent drug that comprises flos carthami and contain safflower of detection method Detection and Extraction method of golden yellow powder wherein.
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| CN103076417A (en) * | 2012-12-13 | 2013-05-01 | 东北石油大学 | Method for synchronously extracting organic pollutants in water sample |
| CN103728254A (en) * | 2013-12-20 | 2014-04-16 | 广西中烟工业有限责任公司 | Method for rapidly detecting golden yellow powder in packaging paper |
| CN108333285A (en) * | 2018-01-10 | 2018-07-27 | 广西壮族自治区食品药品检验所 | Red, yellow based dye inspection method in Xiao Ke Lin piece and Xiaokelin capsule for diabetes |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103076417A (en) * | 2012-12-13 | 2013-05-01 | 东北石油大学 | Method for synchronously extracting organic pollutants in water sample |
| CN103076417B (en) * | 2012-12-13 | 2017-03-22 | 东北石油大学 | Method for synchronously extracting organic pollutants in water sample |
| CN103728254A (en) * | 2013-12-20 | 2014-04-16 | 广西中烟工业有限责任公司 | Method for rapidly detecting golden yellow powder in packaging paper |
| CN103728254B (en) * | 2013-12-20 | 2016-06-29 | 广西中烟工业有限责任公司 | A kind of method of Acid orange Ⅱ in quick detection wrapping paper |
| CN108333285A (en) * | 2018-01-10 | 2018-07-27 | 广西壮族自治区食品药品检验所 | Red, yellow based dye inspection method in Xiao Ke Lin piece and Xiaokelin capsule for diabetes |
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Application publication date: 20120725 |