CN106645477A - Method for detecting florfenicol amine residue and application - Google Patents
Method for detecting florfenicol amine residue and application Download PDFInfo
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- CN106645477A CN106645477A CN201611193127.5A CN201611193127A CN106645477A CN 106645477 A CN106645477 A CN 106645477A CN 201611193127 A CN201611193127 A CN 201611193127A CN 106645477 A CN106645477 A CN 106645477A
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- florfenicol amine
- acetonitrile
- florfenicol
- ethyl acetate
- amine
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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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/14—Preparation by elimination of some components
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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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
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Abstract
The invention relates to the field of veterinary drug residue detection, and in particular relates to a method for detecting a florfenicol amine residue. The method comprises the steps of extracting the florfenicol amine residue in a sample by using acetonitrile-ethyl acetate, and then detecting the florfenicol amine residue by using a high performance liquid chromatograph-mass spectrometer, wherein the acetonitrile ethyl acetate is formed by mixing acetonitrile with ethyl acetate in the volume ratio of 1:1. The sample is extracted and purified and then the florfenicol amine residue is detected by using the high performance liquid chromatograph-mass spectrometer. The method is wide in matrix coverage, simple and convenient to operate, high in sensitivity, good in repeatability and low in detection limit; impurity contamination is greatly reduced, the protectiveness on an instrument and a chromatographic column is large, and maintenance and reproducibility of the instrument are greatly improved.
Description
Technical field
The invention belongs to field of veterinary drug residue detection, and in particular to method and answer that a kind of detection florfenicol amine is remained
With.
Background technology
At present, for animal-derived food detect method that florfenicol amine adopts mostly for：ELISA is efficient
Liquid chromatography, these method detections are limited to 1mg/kg or higher, and some employing liquid matter methods are analyzed, pre-treatment C18
Post or the distribution purification of liquid liquid, impurity purification is not thoroughly and just for single-matrix：Egg, matrix covers not comprehensive, it is impossible to suitable
Answer practical application request.
The content of the invention
For the problems of the prior art, it is an object of the invention to provide a kind of be directed to various matrix, easy to operate, spirit
The method of the detection florfenicol amine residual that sensitivity is high, reproducible, test limit is low.
To reach object above, the present invention is adopted the technical scheme that：
A kind of method of detection florfenicol amine residual, using acetonitrile ethyl acetate florfenicol amine residual in sample is extracted
Thing, afterwards using high performance liquid chromatography GC-MS detection florfenicol amine residual；The acetonitrile ethyl acetate be acetonitrile and
Ethyl acetate is mixed by 1: 1 volume ratio.
On the basis of such scheme, the method and step of the detection florfenicol amine residual is as follows：
1) extraction purification
2.00g samples are weighed, adds 15mL acetonitrile ethyl acetate, ultrasonic 20min, 4000r/min centrifugation 5min to take supernatant
Liquid, repeats and merge twice supernatant in heart bottle, and the acetic acid solutions of 3mL 5%, rotation are added in supernatant after merging
Steam to without backflow；Pour remaining liq into centrifuge tube, then cleaned with 4mL5% acetic acid solutions and poured into centrifuge tube after heart bottle；Plus
Enter 10mL n-hexanes, vortex oscillation 1min, 4000r/min centrifugation 5min remove n-hexane layer, and extract is standby；
2) column purification is purified
After 2mL methyl alcohol and 2mL water balances activation PCX decontaminating columns, loading, with 3mL5% formic acid methanol solutions drip washing 2 times,
Drain；Then eluted with 6mL20% ammoniacal liquor methanol solution, receive eluent, rotated to dry；2mL methanol aqueous solutions are added to be vortexed
Constant volume；0.22 μm of filter membrane is crossed, it is to be measured；
3) using high performance liquid chromatography GC-MS detection florfenicol amine residual
Chromatographic parameter is：Chromatographic column：1.8 μm of XDB-C18,4.6mm*50mm；Column temperature：40 degree；Flow velocity：0.3mL/min；
Sample size：2μL；Mobile phase is：A：0.1% formic acid water, B：Methyl alcohol；
Mass spectrometry parameters are：Ion gun：ESI sources+；Gas Temp：300℃；Gas Flow：10L/min；Nebulizer：
45psi；Sheath Gas Tem：375℃：Sheath Gas flow：11L/min.
On the basis of such scheme, it is described detection florfenicol amine residual method be applied to detect animal derived food
The residual of middle florfenicol amine.
On the basis of such scheme, the animal derived food is muscle, liver, milk and eggs.
Beneficial effects of the present invention：
Present invention florfenicol amine to be detected belongs to polar compound, and acetonitrile polarity is also very big, is mixed according to similar
Principle, with pure acetonitrile extract sample polar impurity it is many, so as to disturb the purification of florfenicol amine, and ethyl acetate belongs to inclined
The material of low pole, by the use of both mixing as Extraction solvent, can improve the extraction efficiency of target compound, and pole can be reduced again
The interference of property impurity；Add 5% acetic acid aqueous solution to make florfenicol amine into ionic condition during revolving, dissolve in aqueous,
PCX decontaminating columns are crossed for next step to prepare；N-hexane is non-polar solven, and addition n-hexane can be by the non-pole in matrix in extraction
Property impurity is further extracted；PCX decontaminating columns have benzene sulfonic acid type functional group, and the florfenicol amine of adsorbable ionization is used
5% formic acid methanol solution drip washing, can further remove the polar impurity in matrix；Ammoniacal liquor methanol solution has higher ion strong
Degree, can replace florfenicol amine from PCX decontaminating columns during wash-out.
This method carries out Instrumental Analysis using UPLC-MSMS, and matrix covers the animal sources such as muscle, liver, milk, eggs food
Product, it is 1 μ g/kg that detection limit is low；Acetonitrile ethyl acetate is extracted used in the present invention, n-hexane removal of impurities, compared to its other party
Method, it is easy to operate；Using PCX solid-phase extraction columns, selective strong, the rate of recovery is high, effectively goes the removal of impurity；Using high performance liquid chromatography
GC-MS, and using multiple-reaction monitoring (MRM) acquisition method, compared to single high performance liquid chromatography, with sensitivity
The low advantage of high, reproducible, test limit, and greatly reduce impurity interference, this is big to instrument and chromatographic column protectiveness, makes instrument
The maintenance of device and reappearance are greatly improved.
Description of the drawings
The efficient liquid phase mass spectrogram of Fig. 1 florfenicol amines, wherein ordinate are response, and abscissa is m/z；
The measure of Fig. 2 florfenicol amine retention times, wherein ordinate are response, and abscissa is retention time；
The quantitative limit of Fig. 3 florfenicol amines is determined, and wherein ordinate is response, and abscissa is retention time, 3 figures are upper,
In, the lower S/N for representing 3 daughter ions respectively.
The calibration curve of Fig. 4 florfenicol amines, wherein ordinate are peak area response, and abscissa is that florfenicol amine is dense
Degree.
Specific embodiment
The term for being used in the present invention, unless otherwise specified, typically has those of ordinary skill in the art usual
The implication of understanding.
With reference to specific embodiment, and with reference to the data further detailed description present invention.Following examples are simply
The present invention is illustrated, rather than limits the scope of the present invention by any way.
Embodiment
1. the preparation of standard liquid
The preparation of 1.1 storing solutions
Precise 10.00mg florfenicol amines, in being dissolved into methyl alcohol, constant volume to 10mL, as the deposit of 1000 μ g/mL
Liquid (actual concentrations should be multiplied by the purity of florfenicol amine), be placed in 4 DEG C it is stored refrigerated；
The preparation of interstitial fluid in 1.2 standards
1mL florfenicol amines are accurately measured, in being dissolved into methyl alcohol, constant volume to 10mL, as the storing solution of 100 μ g/mL, is put
It is stored refrigerated in 4 DEG C；
The preparation of 1.3 standard working curves
Be configured to 1 with interstitial fluid in standard, 2,5,10, the standard liquid of 20ng/mL is (with methyl alcohol+water (v/v=1:1) constant volume), make
For the standard liquid of working curve.
2. sample treatment
2.1 extraction purifications
Accurate weighing 2.00g ± 0.01g samples add 15mL acetonitrile ethyl acetate (v/v=1 in 50mL centrifuge tubes:1),
Ultrasonic 20min, 4000r/min are centrifuged 5min, take supernatant in 100mL heart bottles, repeat and merge twice supernatant, plus
Enter the acetic acid solutions of 3mL 5%, rotate to without backflow.Pour remaining liq into new 50mL centrifuge tubes, then with the acetic acid solutions of 4mL 5%
The heart bottle is cleaned, and is poured into new 50mL centrifuge tubes.Add 10mL n-hexanes, vortex oscillation 1min, 4000r/min centrifugations
5min, removes n-hexane layer, and extract is standby.
2.2 purification column purifications
After with 2mL methyl alcohol and 2mL water balances activation PCX decontaminating columns, said extracted liquid is added in PCX decontaminating columns and is purified,
And with 3mL5% formic acid methanol solutions drip washing 2 times, drain.Then eluted with the ammoniacal liquor methanol solutions of 6mL 20%, receive eluent,
Rotate to dry.Add 2mL methanol aqueous solution (v/v=1:1) vortex constant volume.0.22 μm of filter membrane is crossed, it is to be measured.
3. high performance liquid chromatography GC-MS detects florfenicol amine residual quantity
The high performance liquid chromatography GC-MS for using is Agilent LC-MSMS 1290/6460, and chromatographic parameter is：Color
Spectrum post：1.8 μm of XDB-C18,4.6mm*50mm；Column temperature：40 degree；Flow velocity：0.3mL/min；Sample size：2μL；Mobile phase is：A：
0.1% formic acid water, B：Methyl alcohol；The gradient of mobile phase is as shown in table 1：
The eluent gradient of table 1
| Time(min) | B% |
| 0.00 | 20 |
| 1.00 | 20 |
| 3.00 | 90 |
| 4.00 | 90 |
| 4.01 | 20 |
| 5.50 | 20 |
Mass spectrometry parameters are：Ion gun：ESI sources+；Gas Temp：300℃；Gas Flow：10L/min；Nebulizer：
45psi；Sheath Gas Tem：375℃：Sheath Gas flow：11L/min.
4. result and analysis
4.1 specificities
As shown in figure 1, machine on 1ppm florfenicol amines, by mass spectrum optimization 3 ion pairs are respectively obtained, wherein ordinate is
Response, abscissa is m/z.
Mass spectral results are as shown in table 2：
The mass spectral results of table 2
50ppb florfenicol amines determine retention time by C18 chromatogram post separations.As shown in Fig. 2 retention time is about
1.5min, and the peak shape of chromatogram is preferably, noiseless peak occurs.
4.2 quantitative limits
Add the standard items for containing 1.0 μ g/kg equivalent to sample in matrix, machine testing in premenstrual process calculates its letter
Make an uproar than (S/N) ＞ 10, as shown in Figure 3.
Measure the quantitative limit of the method：1.0μg/kg.
4.3 calibration curves
Precision draws florfenicol amine standard items, and it is 2,5,10,20 to be diluted to series concentration with 50% methanol aqueous solution,
50ng/mL standard liquids, difference sample introduction is determined, and with peak area response as ordinate, florfenicol amine concentration is abscissa, is drawn
Calibration curve is as shown in Figure 4：The regression equation for obtaining florfenicol amine is Y=2970.653983*X-2691.191137, R2=
0.9996, from coefficient correlation, in 2ng/mL～50ng/mL calibration curve ranges of linearity, UPLC-MSMS methods determine linear
Relation is good, and this calibration curve can be used for accurate quantitative analysis.
The addition of 4.4 blank samples is reclaimed
Blank sample addition reclaims as shown in table 3：
The addition of the blank sample of table 3 is reclaimed
Addition is reclaimed and chooses the high pork of fat content on market, low beef, egg, duck liver, the milk of supermarket's purchase
Quality Control experiment is done, the rate of recovery illustrates that this method has good stability between 70%-95%.
5. conclusion
By being measured to the florfenicol amine in animal sources matrix with UPLC-LCMSMS methods, it is determined that using acetonitrile：Second
Acetoacetic ester=1:1 volume ratio is extracted, and PCX pillars are purified, and florfenicol amine chromatographic peak can be made to reach baseline separation,
Peak shape is good, and test limit is low, and sensitivity is high, reclaims stable, and the present invention is the florfenicol amine residual quantity in animal sources matrix
Measure establishes a kind of reliably analysis method.
Claims (4)
1. a kind of method that detection florfenicol amine is remained, it is characterised in that：Fluorobenzene in sample is extracted using acetonitrile ethyl acetate
Buddhist nun examines amine residue, detects florfenicol amine residual quantity using high performance liquid chromatography GC-MS afterwards；The acetonitrile acetic acid
Ethyl ester is that acetonitrile and ethyl acetate are mixed by 1: 1 volume ratio.
2. the method for detecting florfenicol amine residual according to claim 1, it is characterised in that：Step is as follows：
1) extraction purification
2.00g samples are weighed, add 15mL acetonitrile ethyl acetate, ultrasonic 20min, 4000r/min centrifugation 5min to take supernatant,
Repeat twice merge supernatant in heart bottle, in supernatant after merging add the acetic acid solutions of 3mL 5%, rotate to
Without backflow；Pour remaining liq into centrifuge tube, then cleaned with the acetic acid solutions of 4mL 5% and poured into centrifuge tube after heart bottle；Add
10mL n-hexanes, vortex oscillation 1min, 4000r/min centrifugation 5min remove n-hexane layer, and extract is standby；
2) column purification is purified
After with 2mL methyl alcohol and 2mL water balances activation PCX decontaminating columns, loading, with 3mL5% formic acid methanol solutions drip washing 2 times, is taken out
It is dry；Then eluted with the ammoniacal liquor methanol solutions of 6mL 20%, receive eluent, rotated to dry；2mL methanol aqueous solutions are added to be vortexed fixed
Hold；0.22 μm of filter membrane is crossed, it is to be measured；
3) using high performance liquid chromatography GC-MS detection florfenicol amine residual
Chromatographic parameter is：Chromatographic column：1.8 μm of XDB-C18,4.6mm*50mm；Column temperature：40 degree；Flow velocity：0.3mL/min；Sample introduction
Amount：2μL；Mobile phase is：A：0.1% formic acid water, B：Methyl alcohol；
Mass spectrometry parameters are：Ion gun：ESI sources+；Gas Temp：300℃；Gas Flow：10L/min；Nebulizer：45psi；
Sheath Gas Tem：375℃：Sheath Gas flow：11L/min.
3. detection florfenicol amine according to claim 1 or claim 2 remains the application of method, it is characterised in that：It is dynamic for detecting
The residual of florfenicol amine in thing derived food.
4. detect that florfenicol amine remains the application of method according to claim 3, it is characterised in that：The animal derived food
Product are muscle, liver, milk and eggs.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611193127.5A CN106645477B (en) | 2016-12-21 | 2016-12-21 | A kind of remaining method of detection florfenicol amine and application |
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| CN201611193127.5A CN106645477B (en) | 2016-12-21 | 2016-12-21 | A kind of remaining method of detection florfenicol amine and application |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108760938A (en) * | 2018-08-01 | 2018-11-06 | 扬州大学 | Chloramphenicol, Thiamphenicol, Florfenicol and its how remaining analysis method of metabolite florfenicol amine in a kind of efficient detection birds, beasts and eggs |
| CN110108826A (en) * | 2019-05-24 | 2019-08-09 | 内蒙古蒙牛乳业（集团）股份有限公司 | The detection method of florfenicol amine in cream or dairy products |
| CN112345661A (en) * | 2020-10-21 | 2021-02-09 | 北京精益捷检测科技有限公司 | Method for determining content of florfenicol in veterinary drug gardenia flaviviridae oral liquid |
| CN112461823A (en) * | 2020-11-10 | 2021-03-09 | 苏州慧源安食检测科技有限公司 | Rapid detection method of florfenicol |
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| CN101726553A (en) * | 2009-12-22 | 2010-06-09 | 扬州大学 | Method for detecting thiamphenicol, florfenicol and residues of metabolite florfenicol amine in egg simultaneously |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108760938A (en) * | 2018-08-01 | 2018-11-06 | 扬州大学 | Chloramphenicol, Thiamphenicol, Florfenicol and its how remaining analysis method of metabolite florfenicol amine in a kind of efficient detection birds, beasts and eggs |
| CN110108826A (en) * | 2019-05-24 | 2019-08-09 | 内蒙古蒙牛乳业（集团）股份有限公司 | The detection method of florfenicol amine in cream or dairy products |
| CN112345661A (en) * | 2020-10-21 | 2021-02-09 | 北京精益捷检测科技有限公司 | Method for determining content of florfenicol in veterinary drug gardenia flaviviridae oral liquid |
| CN112345661B (en) * | 2020-10-21 | 2022-11-15 | 北京精益捷检测科技有限公司 | Method for determining content of florfenicol in veterinary drug gardenia flaviviridae oral liquid |
| CN112461823A (en) * | 2020-11-10 | 2021-03-09 | 苏州慧源安食检测科技有限公司 | Rapid detection method of florfenicol |
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| CN106645477B (en) | 2018-11-06 |
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