CN101598713B - Method for detecting diethylstilbestrol - Google Patents
Method for detecting diethylstilbestrol Download PDFInfo
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- CN101598713B CN101598713B CN2009100528897A CN200910052889A CN101598713B CN 101598713 B CN101598713 B CN 101598713B CN 2009100528897 A CN2009100528897 A CN 2009100528897A CN 200910052889 A CN200910052889 A CN 200910052889A CN 101598713 B CN101598713 B CN 101598713B
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Abstract
A method for detecting diethylstilbestrol belongs to the field of analytical chemistry, wherein the method includes the followings: pre-treating the sample to be detected, preparing the sample solution and then carrying out the following treatments: adding sample solution at one end point of the paper chromatography strip; placing the paper chromatography strip in the normal hexane-ethanol developing solvent; taking out the paper chromatography strip when the front end of the developing solvent is adjacent to the front end of the paper chromatography strip; air-drying, wherein the normal hexane-ethanol developing solvent by volume includes: 1 to 20 parts of normal hexane, 0.1 to 5 parts of ethanol; spraying the potassium ferricyanide-ferric trichloride-H2O2 on the chromatography strip; color displaying, wherein the potassium ferricyanide-ferric trichloride-H2O2 is as follows: mixing the 0.01 to 5 mol/L aqueous solution of the potassium ferricyanide and the 0.01 to 5 mol/L aqueous solution of ferric trichloride evenly; then adding 0.001% to 5% of the H2O2 by volume 1 to 1; and the volume of the H2O2 is 0 to 10% of the total volume of the solution. The invention has the advantages of simple method and device, fast detecting speed and low detecting cost, and can be used for fastly detecting the DES in food on the spot.
Description
Technical field
The present invention relates to a kind of detection method of chemical technology field, specifically is the method for a kind of detection diethylstilbestrol (DES).
Background technology
(Diethylstilbestrol DES) is born in the forties in 20th century to diethylstilbestrol, is a kind of synthetic estrogen with phenolic hydroxyl structure, and cis and trans two kinds of isomeride are arranged, and wherein trans physiologically active is stronger.Because DES has the weightening finish of the animal of promotion, increase effect proteins deposited and the minimizing fat deposition, once be widely used in promoting growth of animal, increased lean meat percentage, improved food conversion ratio.The later stage seventies 20th century is owing to find that DES has reproduction and genetoxic (comprising carcinogenic and teratogenesis).Therefore, the U.S. banned use of the growth accelerator of DES as food animal since 1979, European Union banned use of DES to be used for the food that animal that food animal and limiting inlet other countries used this medicine produces from 1986, provide against use DES in No. 176 bulletin of China Ministry of Agriculture in 2002 and No. 193 bulletin.On April 4th, 2004, The Ministry of Agriculture of the People's Republic of China, MOA's issue " 2003 annual animal product veterinary drug residue Supervisory Surveillance Program " (agriculture and animal husbandry is sent out [2003] No. 6) requires zero to detect in animal food to diethylstilbestrol.But the illegal DES situation of adding occurs frequently in livestock breeding industry, the residue detection of diethylstilbestrol in the food is caused great attention both domestic and external, thereby set up fast, and the sensitive and method that can realize on-the-spot detection diethylstilbestrol is necessity very.
The method that present domestic and foreign literature report is used for the DES residue detection is a lot, mainly contains immunological method: radioimmunology (RIA), euzymelinked immunosorbent assay (ELISA) (ELISA) etc.; Chromatographia method: as high performance liquid chromatography (HPLC), high performance liquid chromatography-tandem mass detection method (HPLC-MS), vapor-phase chromatography (GC), GC-MS(gas chromatography-mass spectrography) (GC-MS), thin-layered chromatography (TLC) etc.; Additive method: as cyclic voltammetry, spectrophotometric method, fluorescence spectrophotometry analytic approach, capillary electrophoresis, portable injection chemiluminescence analysis method and bioanalysis etc.In these methods, high efficiency liquid phase chromatographic analysis method is the assay method of diethylstilbestrol in the GB/T14931.2-1994 livestock and poultry meat, this method have sensitivity, accurately, accurate, impurity disturbs fewly, has advantages such as higher repeatability, authority.But this method also has, and experimental apparatus costliness, maintenance practices complexity, equipment are higher to environmental requirement, technology content is higher, reagent toxicity is big, single sample detects shortcomings such as cost is higher, sample pre-treatments complexity; Gas chromatography-mass spectrography, the vapor-phase chromatography of radioimmunology and charged sub-acquisition detector be at present existing can be effective, measure the horizontal content detecting method of DES ppb delicately, but because diethylstilbestrol has polarity, and boiling point is higher, need loaded down with trivial details derivatization step, thereby limited the application of gas chromatographic analysis.More than these analytical approachs all need large-sized analytic instrument, operating process is loaded down with trivial details, can not realize on-the-spot the detection.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of method that detects diethylstilbestrol is provided.It is simple that the present invention has a method and apparatus, and detection speed is fast and detect low cost and other advantages, can be used for quick on-the-spot detection of DES in the food.
The present invention is achieved by the following technical solutions,
Testing sample is carried out pre-service, the preparation sample solution, carry out following processing then:
Step 1 adds sample solution at an end points of paper chromatography strip;
Step 2 places the paper chromatography strip in normal hexane-ethanol developping agent, when solvent front during near paper chromatography strip forward position, takes out the paper chromatography strip, and is air-dry;
Described normal hexane-ethanol developping agent is: by volume calculates, and 1～20 part of normal hexane, 0.1～5 part of ethanol mixes and gets;
Step 3 is with the potassium ferricyanide-ferric trichloride-H
2O
2Be sprayed on the chromatography strip colour developing;
The described potassium ferricyanide-ferric trichloride-H
2O
2For: be by volume 1: 1 the aqueous solution of the ferric trichloride of the aqueous solution of the potassium ferricyanide of 0.01～5Mole/L and 0.01～5Mole/L is even, add massfraction again and be 0.001%～5% H
2O
2, wherein add H
2O
2Volume account for 0～10% of overall solution volume.
Described sample solution is bird or domestic animals sample solution.
In the step 1, described point adds and is specially, and at 1～2cm place of paper chromatography strip one end, adds sample solution with sample introduction kapillary point, makes sample solution become the round dot that diameter is 3～7mm on the paper chromatography strip.
In the step 2, described near being specially, when solvent front apart from paper chromatography strip forward position 1～2cm.
In the step 3, described colour developing is specially, and spraying massfraction before the colour developing on chromatography strip again is 1% glacial acetic acid.
The present invention utilizes the reductibility of diethylstilbestrol phenolic hydroxyl group, makes the potassium ferricyanide-ferric trichloride test solution generate Prussian blue precipitation, and this is deposited in the strongly acidic solution and dissolves.
The present invention has following beneficial effect: it is simple that the present invention has a method and apparatus, and detection speed is fast and detect low cost and other advantages, can be used for quick on-the-spot detection of DES in the food.
Embodiment
Present embodiment has provided detailed embodiment and process being to implement under the prerequisite with the technical solution of the present invention, but protection scope of the present invention is not limited to following embodiment.The experimental technique of unreceipted actual conditions in the following example, usually according to normal condition, or the condition of advising according to manufacturer.
Embodiment 1
Take by weighing the new fresh chicken meat that 5g rubs, put into tool plug centrifuge tube, add 10ml ethanol, ultrasonic water bath heating 30min in the centrifugal 10min of 3000rpm, removes supernatant, add 10ml ethanol in the residue again, the even back vibration 20min that is mixed is in the centrifugal 10min of 3000rpm, merge supernatant twice, become turbid this moment, needs centrifugal once more 10min, get supernatant and cross microfiltration membranes,, shake up with deionized water constant volume 10ml, numbering places 4 ℃ of refrigerators standby respectively.At the about 1.5cm of the end place of paper chromatography strip, with sample introduction kapillary point sample solution, every once, adds some points twice again, makes it become the round dot of the about 5mm of diameter, and point sample finishes, and solvent is freely volatilized.Get normal hexane-ethanolic solution 10ml in chromatography cylinder, normal hexane-ethanol developping agent is: by volume calculate, and 10 parts of normal hexanes, 1 part of ethanol mixes and gets; The paper chromatography strip of having put sample is stood in the chromatography cylinder, build chromatography cylinder, up exhibition layer when solvent front during apart from paper chromatography strip forward position upper end 1～2cm, takes out the paper chromatography strip, and is air-dry.To mix the developer potassium ferricyanide-ferric trichloride-H with glass spray bottle
2O
2Be sprayed on the air-dry chromatography strip potassium ferricyanide-ferric trichloride-H
2O
2For: be by volume 1: 1 the aqueous solution of the ferric trichloride of the aqueous solution of the potassium ferricyanide of 1.0Mole/L and 1.0Mole/L is even, add massfraction again and be 3% H
2O
2, wherein add H
2O
2Volume account for 9% of overall solution volume.
The result does not show coloured speckle, adds 10 in sample solution
-6The diethylstilbestrol standard solution of M is used with quadrat method and is detected, and shows coloured speckle on the paper chromatography strip.
Embodiment 2
Take by weighing the fresh pork that 5g rubs, put into tool plug centrifuge tube, add 10ml ethanol, ultrasonic water bath heating 30min in the centrifugal 10min of 3000rpm, removes supernatant, add 10ml ethanol in the residue again, the even back vibration 20min that is mixed is in the centrifugal 10min of 3000rpm, merge supernatant twice, become turbid this moment, needs centrifugal once more 10min, get supernatant and cross microfiltration membranes,, shake up with deionized water constant volume 10ml, numbering places 4 ℃ of refrigerators standby respectively.At the about 1.5cm of the end place of paper chromatography strip, with sample introduction kapillary point sample solution, every once, adds some points twice again, makes it become the round dot of the about 5mm of diameter, and point sample finishes, and solvent is freely volatilized.Get normal hexane-ethanolic solution 10ml in chromatography cylinder, normal hexane-ethanol developping agent is: by volume calculate, and 8 parts of normal hexanes, 0.5 part of ethanol mixes and gets; The paper chromatography strip of having put sample is stood in the chromatography cylinder, build chromatography cylinder, up exhibition layer when solvent front during apart from paper chromatography strip forward position upper end 1～2cm, takes out the paper chromatography strip, and is air-dry.To mix the developer potassium ferricyanide-ferric trichloride-H with glass spray bottle
2O
2Be sprayed on the air-dry chromatography strip potassium ferricyanide-ferric trichloride-H
2O
2For: be by volume 1: 1 the aqueous solution of the ferric trichloride of the aqueous solution of the potassium ferricyanide of 0.5Mole/L and 0.5Mole/L is even, add massfraction again and be 0.3% H
2O
2, wherein add H
2O
2Volume account for 2% of overall solution volume.
The result shows, contains the diethylstilbestrol of at least 0.5 μ g/g in the sample.
Embodiment 3
Take by weighing the fresh beef that 5g rubs, put into tool plug centrifuge tube, add 10ml ethanol, ultrasonic water bath heating 30min in the centrifugal 10min of 3000rpm, removes supernatant, add 10ml ethanol in the residue again, the even back vibration 20min that is mixed is in the centrifugal 10min of 3000rpm, merge supernatant twice, become turbid this moment, needs centrifugal once more 10min, get supernatant and cross microfiltration membranes,, shake up with deionized water constant volume 10ml, numbering places 4 ℃ of refrigerators standby respectively.At the about 1.5cm of the end place of paper chromatography strip, with sample introduction kapillary point sample solution, every once, adds some points twice again, makes it become the round dot of the about 5mm of diameter, and point sample finishes, and solvent is freely volatilized.Get normal hexane-ethanolic solution 10ml in chromatography cylinder, by volume calculate, 5 parts of normal hexanes, 0.1 part of ethanol mixes and gets; The paper chromatography strip of having put sample is stood in the chromatography cylinder, build chromatography cylinder, up exhibition layer when solvent front during apart from paper chromatography strip forward position upper end 1～2cm, takes out the paper chromatography strip, and is air-dry.To mix the developer potassium ferricyanide-ferric trichloride-H with glass spray bottle
2O
2Be sprayed on the air-dry chromatography strip potassium ferricyanide-ferric trichloride-H
2O
2For: be by volume 1: 1 the aqueous solution of the ferric trichloride of the aqueous solution of the potassium ferricyanide of 1.0Mole/L and 1.0Mole/L is even, add massfraction again and be 0.01% H
2O
2, wherein add H
2O
2Volume account for 0.1% of overall solution volume.
The result shows, contains the diethylstilbestrol of at least 0.5 μ g/g in the sample.
Claims (4)
1. a method that detects diethylstilbestrol is carried out pre-service with testing sample, and the preparation sample solution carries out following processing, it is characterized in that, comprises the steps:
Step 1 adds sample solution at an end points of paper chromatography strip;
Step 2 places the paper chromatography strip in normal hexane-ethanol developping agent, when solvent front during near paper chromatography strip forward position, takes out the paper chromatography strip, and is air-dry;
Described normal hexane-ethanol developping agent obtains by in following three kinds of modes any one:
A) by volume calculate, 10 parts of normal hexanes, 1 part of ethanol mixes and gets;
B) by volume calculate, 8 parts of normal hexanes, 0.5 part of ethanol mixes and gets;
C) by volume calculate, 5 parts of normal hexanes, 0.1 part of ethanol mixes and gets;
Step 3 is with the potassium ferricyanide-ferric trichloride-H
2O
2Be sprayed on the chromatography strip colour developing;
The described potassium ferricyanide-ferric trichloride-H
2O
2For: be by volume 1: 1 the aqueous solution of the ferric trichloride of the aqueous solution of the potassium ferricyanide of 0.01～5Mole/L and 0.01～5Mole/L is even, add massfraction again and be 0.001%～5% H
2O
2Solution, wherein H
2O
2The volume of solution accounts for 0～10% of overall solution volume;
Described sample solution is bird or domestic animals sample solution.
2. the method for detection diethylstilbestrol according to claim 1 is characterized in that, in the step 1, described point adds and is specially, at 1～2cm place of paper chromatography strip one end, add sample solution with sample introduction kapillary point, make sample solution on the paper chromatography strip, become the round dot that diameter is 3～7mm.
3. the method for detection diethylstilbestrol according to claim 1 is characterized in that, and is described near being specially in the step 2, when solvent front apart from paper chromatography strip forward position 1～2cm.
4. the method for detection diethylstilbestrol according to claim 1 is characterized in that, in the step 3, described colour developing is specially, and spraying massfraction before the colour developing on chromatography strip again is 1% glacial acetic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100528897A CN101598713B (en) | 2009-06-11 | 2009-06-11 | Method for detecting diethylstilbestrol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100528897A CN101598713B (en) | 2009-06-11 | 2009-06-11 | Method for detecting diethylstilbestrol |
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| CN101598713B true CN101598713B (en) | 2011-07-27 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102175792B (en) * | 2010-12-24 | 2012-04-25 | 北京师范大学 | Method for detecting estrogen, nonyl phenol, octylphenol and bisphenol A together in water environment |
| CN102262125B (en) * | 2011-07-28 | 2013-10-09 | 南京师范大学 | Electrochemical immune sensor for detecting diethylstilbestrol and preparation method and application of sensor |
| CN102443285B (en) * | 2011-09-05 | 2013-07-24 | 福州坤彩精化有限公司 | Prussian blue pearlescent pigment and preparation method thereof |
| CN106770237A (en) * | 2016-12-07 | 2017-05-31 | 无锡艾科瑞思产品设计与研究有限公司 | A kind of diethylstilbestrol detection method and detection card |
| CN107084975A (en) * | 2017-04-13 | 2017-08-22 | 东莞市食品药品检验所 | The quick detection reagent and its detection method of a kind of Indomethacin |
| CN107260707A (en) * | 2017-08-11 | 2017-10-20 | 上海凌凯医药科技有限公司 | It is a kind of to be used to deliver targeted nano particulate vector of bladder cancer medicine and its preparation method and application |
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