CN108982681A - The detection method of lincomycin in a kind of cow's milk - Google Patents
The detection method of lincomycin in a kind of cow's milk Download PDFInfo
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- CN108982681A CN108982681A CN201810546015.6A CN201810546015A CN108982681A CN 108982681 A CN108982681 A CN 108982681A CN 201810546015 A CN201810546015 A CN 201810546015A CN 108982681 A CN108982681 A CN 108982681A
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- lincomycin
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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
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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
- G01N2030/042—Standards
- G01N2030/047—Standards external
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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
Abstract
The present invention relates to field of detection of food safety, the detection method of lincomycin in specially a kind of cow's milk fast and accurately carries out qualitative and quantitative analysis to the lincomycin of Residues in Milk by Liquid Chromatography-Tandem Mass Spectrometry.The detection method of lincomycin, by the way that sample is carried out second extraction through acetonitrile, and is added n-hexane in extracting solution, removes fat therein, be measured by ultra performance liquid chromatography-tandem mass spectrometry to the detection of lincomycin in cow's milk in a kind of cow's milk.
Description
Technical field
The present invention relates to field of detection of food safety, the detection method of lincomycin in specially a kind of cow's milk.
Background technique
Lincomycin (lincomycin, LIN) is also known as lincomycinum, cillimycin, is to be fermented to generate by streptomyces lincolnensis
Lincosamides mainly have stronger antibacterial action to gram-positive bacteria, certain anaerobic bacterias and mycoplasma, but to leather
Lan Shi negative bacterium is invalid.It is commonly used for feed addictive or is directly injected into treating cow mammitis, two kinds of administration modes all can
Residual of the lincomycin in cow's milk is caused, after cow breast perfusion administration, drains main (about 50% or more) through cream
Gland is discharged with milk, so as to cause the medicament residue in cow's milk there are higher concentration.Remaining lincomycin passes through food in cow's milk
Object chain can cause renal dysfunction and gram-positive bacteria drug resistance to increase after entering human body.Therefore, People's Republic of China's agriculture
It is 150 μ g/kg that industry portion 235, which announces and defines the maximum residue limit of lincomycin in milk,.One is established for this reason, it may be necessary to study
Kind of pre-treatment is simple, lincomycin method for detecting residue in high sensitivity, favorable reproducibility milk, so as to can be fast and accurately
Qualitative and quantitative analysis is carried out to the lincomycin of Residues in Milk, to guarantee the product quality of milk.
Currently, the relevant criterion for the lincomycin residues detection method that China has formulated have SN/T2218-2008 " into
Export LIN Kesheng medicament residue quantity measuring method liquid chromatography mass/mass spectrography in animal-derived food " and GB/T
" 4789.27-2008 antibiotic residue is examined in food hygiene Micro biological Tests fresh milk ".Former approach is although with higher
Selectivity, can be confirmed according to the structural information of acquisition, but relatively high to the operating process of pre-treatment requirement, and sensitivity
Relatively low, testing cost is higher.Although later approach testing cost is lower, pretreatment process is complicated, and reproducibility is poor.
In addition, in cow's milk reported in the literature lincomycin method for detecting residue there are also high performance liquid chromatography, gas chromatography, enzyme-linked exempt from
Epidemic disease absorption method (ELISA), colloidal gold immuno-chromatography test paper strip method.High performance liquid chromatography and gas chromatography pretreatment process are multiple
It is miscellaneous, and can not be accurate qualitative.Enzyme linked immunosorbent assay (ELISA) and colloidal gold immuno-chromatography test paper strip method it is although easy to operate,
Quickly, but it is only suitable for the screening of great amount of samples, cannot accurately carries out qualitative and quantitative detection.
Summary of the invention
The present invention provides a kind of detection method of lincomycin in cow's milk, by Liquid Chromatography-Tandem Mass Spectrometry quickly, it is quasi-
The true lincomycin to Residues in Milk carries out qualitative and quantitative analysis, improves the monitoring means of former milk residue of veterinary drug.
The technical solution adopted by the present invention are as follows:
The detection method of lincomycin in a kind of cow's milk, comprising the following steps:
A. sample is taken, with centrifugal treating after acetonitrile vortex mixed, obtains the first supernatant；
B. it will precipitate again with centrifugal treating after acetonitrile vortex mixed, and obtain the second supernatant, by the first supernatant and the
Two supernatants are mixed to get mixing supernatant；
C. centrifugal treating after mixing supernatant being mixed with n-hexane discards n-hexane layer, and lower layer's solution is transferred to chicken
In heart bottle；
D. lower layer's solution is evaporated to and is closely done, wash chicken heart bottle, constant volume with acetonitrile solution；
E. filter membrane after mixing carries out ultra performance liquid chromatography-tandem mass spectrum measurement.
Preferably, 4g sample is weighed in the step a, be placed in 50ml centrifuge tube, 20ml acetonitrile, whirlpool mixing is added
30s, the ultrasonic extraction 10min in ice-water bath, 4 DEG C, 8000r/min is centrifuged 5min.
Preferably, 10ml acetonitrile, whirlpool mixing 30s, the ultrasonic extraction 10min in ice-water bath, 4 are added in the step b
DEG C, 8000r/min is centrifuged 5min.
Preferably, in the step c in mixing supernatant be added 10ml n-hexane, whirlpool mix 1min, 4 DEG C,
8000r/min is centrifuged 5min.
Preferably, 45 DEG C of rotary evaporations of lower layer's solution are done in the step d to close, washs chicken heart bottle with acetonitrile solution
After be settled to 4ml.
Preferably, acetonitrile solution is that acetonitrile is mixed with use for laboratory level-one water according to volume ratio 1:9 in the step d
Close uniform drug solution.
Preferably, 0.22 μm of filter membrane is crossed in the step e.
Preferably, chromatographic condition are as follows:
Chromatographic column: 1.8 μm, 2.1*100mm；
Flow velocity: 0.25ml/min；
Sampling volume: 5 μ l；
Column temperature: 40 DEG C.
Wherein, mobile phase and degree elution time are as follows:
Mobile phase A: volume fraction is 0.1% aqueous formic acid；
Mobile phase B: acetonitrile；
0~0.5min of elution time, Mobile phase B is from 20% linear increase to 85%；
0.5~2.8min of elution time, Mobile phase B keep 85%；
2.8~3.2min of elution time, Mobile phase B are down to 20% from 85%；
3.2~6min of elution time, Mobile phase B keep 20%.
Preferably, Mass Spectrometry Conditions are as follows:
Ion source: electric spray ion source；
Scanning mode: cation scanning；
Detection mode: multiple-reaction monitoring；
Capillary voltage: 3.40KV；
Orifice potential: 41V；
Ion source temperature: 120 DEG C；
Desolvation temperature: 360 DEG C；
Desolventizing gas flow: 650L/h；
Taper hole throughput: 50L/h；
Collision gas flow: 0.15ml/min.
The present invention relates to principles are as follows:
Sample is through acetonitrile precipitation albumen and extracts, and after n-hexane removes fat, is steamed near dry, with acetonitrile solution (1+9)
Constant volume, liquid chromatograph-mass spectrometer measurement, quantified by external standard method.
Used reagent are as follows:
Acetonitrile HPLC Grade matches silent winged scientific and technological (China) Co., Ltd of generation that；
N-hexane HPLC Grade matches silent winged scientific and technological (China) Co., Ltd of generation that；
Formic acid HPLC Grade, ROE SCIENTIFIC INC.；
Lincomycin standard items CAS number: 154-21-2, purity 98.2%, Dr.Ehrenstorfer
Preparation of reagents:
Acetonitrile solution (1+9): it measures 100mL acetonitrile and is added in 900mL level-one water, mix.
Aqueous formic acid (0.1%): taking 1mL formic acid into 1000mL volumetric flask, is settled to scale with level-one water, mixes.
Standard solution is prepared:
Lincomycin standard reserving solution: accurately weighing suitable lincomycin standard items, and being configured to concentration with acetonitrile is 100
The standard reserving solution of μ g/ml.It is kept in dark place in -18 DEG C, validity period 6 months.
Lincomycin standard intermediate fluid: with dilution in acetonitrile being 1- at concentration by lincomycin standard reserving solution as needed
The standard intermediate fluid of 10 μ g/ml.It is kept in dark place in 0-4 DEG C, validity period 3 weeks.
Lincomycin standard working solution: a certain amount of lincomycin standard intermediate fluid is drawn as needed using preceding, uses second
Nitrile aqueous solution (1+9) is diluted to series standard working solution, matching while using step by step.
Instrument and equipment:
Ultra performance liquid chromatography-tandem mass spectrum, UPLC-TQD Waters, US；
Supersonic wave cleaning machine, the Guangzhou JP-C900 jeep ultrasonic electronic equipment Co., Ltd；
Electronic balance AL204, Mettler-Toledo Instrument (Shanghai) Co., Ltd.；
Oscillator MS3BASIC, Guangzhou Yi Ke laboratory technique Co., Ltd；
Rotary Evaporators RV 10BASIC, Guangzhou Yi Ke laboratory technique Co., Ltd；
High speed freezing centrifuge CT15RT, Shanghai Techcomp Instrument Ltd.；
Water purification machine ELIX 10, French MILLIPORE company.
The device have the advantages that being:
1. acetonitrile is selected to be used as Extraction solvent, while extraction can by protein precipitation, by be further centrifuged from
And protein is removed；
2. carrying out second extraction using acetonitrile, the higher rate of recovery can be obtained, makes to extract more complete；
3. n-hexane is added in extracting solution, fat therein is removed by liquid-liquid extraction；
4. compared to being purified by the method for Solid Phase Extraction, this approach simplify pre-treatment step, reduce detect at
This；
5. lincomycin has amine structure, belong to polar compound, thus be suitble to carry out using electrospray ionisation source from
Sonization；
6. being easier to obtain quasi-molecular ion using positive ion mode since lincomycin has alkalescent.
Detailed description of the invention
Fig. 1 is lincomycin full scan mass spectrogram；
Fig. 2 is lincomycin daughter ion scanning mass spectrogram.
Specific embodiment
With reference to the accompanying drawings and examples, a specific embodiment of the invention is described in further detail.
The detection method of lincomycin in a kind of cow's milk, comprising the following steps:
A. 4g sample is weighed, is placed in 50ml centrifuge tube, 20ml acetonitrile is added, whirlpool mixing 30s is ultrasonic in ice-water bath
10min is extracted, 4 DEG C, 8000r/min is centrifuged 5min, shifts supernatant into another 50ml centrifuge tube；
B. it repeats to extract once with 10ml acetonitrile again, merges supernatant in same centrifuge tube；
C. 10ml n-hexane is added in supernatant, whirlpool mixes 1min, and 4 DEG C, 8000r/min is centrifuged 5min, discards just
Lower layer's solution is fully transferred in chicken heart bottle by hexane layer；
D.45 DEG C rotary evaporation is to close dry, with acetonitrile solution (acetonitrile and use for laboratory level-one water according to volume ratio 1:9 into
The uniformly mixed drug solution of row) washing chicken heart bottle, it is settled to 4ml；
E. 0.22 μm of filter membrane is crossed after mixing, and carries out ultra performance liquid chromatography-tandem mass spectrum measurement.
Chromatographic condition:
Chromatographic column: Acquity UPLC HSS T3,1.8 μm, 2.1*100mm；
Mobile phase A: volume fraction is 0.1% aqueous formic acid；
Mobile phase B: acetonitrile；
Flow velocity: 0.25ml/min；
Sampling volume: 5 μ l；
Column temperature: 40 DEG C.
Gradient elution program:
Mobile phase B is 20% when 0min, and 0~0.5min Mobile phase B is linearly increasing to 85%, 0.5~2.8min Mobile phase B
85% is kept, 2.8~3.2min Mobile phase B is down to 20%, and 3.2~6min Mobile phase B keeps 20%.
Mass Spectrometry Conditions:
Ion source: electric spray ion source (ESI)；
Scanning mode: cation scanning；
Detection mode: multiple-reaction monitoring (MRM)；
Capillary voltage: 3.40KV；
Orifice potential: 41V；
Ion source temperature: 120 DEG C；
Desolvation temperature: 360 DEG C；
Desolventizing gas flow: 650L/h；
Taper hole throughput: 50L/h；
Collision gas flow: 0.15ml/min.
The mass spectrometry parameters of lincomycin are shown in Table 1.
Lincomycin has amine structure, belongs to polar compound, therefore is suitble to carry out ion using electrospray ionisation source
Change.Simultaneously as lincomycin has alkalescent, it is easier to obtain quasi-molecular ion using positive ion mode.Therefore, this test
It is measured using ESI+ mode.
As shown in Fig. 1 Fig. 2, full scan is carried out under ESI+ mode, obtains mass spectrogram as shown in Figure 1, m/z407 in Fig. 1
The quasi-molecular ion [M+H] generated for lincomycin ionization+.Orifice potential is advanced optimized, so that the response highest of m/z407.
Using m/z407 as parent ion, daughter ion scanning is carried out, obtains mass spectrogram as shown in Figure 2, as shown in Figure 2 m/z126 and m/z359
It is higher two fragment ions of response that lincomycin quasi-molecular ion passes through that collision obtains, it is possible thereby to determine quota ion
To and qualitative ion pair be respectively 407/126 and 407/359.Again by optimization impact energy, reach the response of two fragment ions
To highest.1 is shown in Table by the Mass Spectrometry Conditions that optimization obtains.
The present invention is five concentration of 1ng/ml, 10ng/ml, 50ng/ml, 100ng/ml, 200ng/ml by compound concentration
The standard solution of point draws standard curve after upper machine testing, and obtaining its linear equation is Y=4966.42*X+229.067, linearly
Correlation coefficient r=0.999975.R > 0.99 meets the phase that method equation of linear regression is confirmed in GB/T27404-2008 annex F
Relationship number is not lower than 0.99 requirement.
1 mass spectrometry parameters of table
It * is quota ion.
Claims (10)
1. the detection method of lincomycin in a kind of cow's milk, it is characterised in that: the following steps are included:
A. sample is taken, with centrifugal treating after acetonitrile vortex mixed, obtains the first supernatant；
B. it will precipitate again with centrifugal treating after acetonitrile vortex mixed, and obtain the second supernatant, it will be on the first supernatant and second
Clear liquid is mixed to get mixing supernatant；
C. centrifugal treating after mixing supernatant being mixed with n-hexane discards n-hexane layer, and lower layer's solution is transferred to chicken heart bottle
In；
D. lower layer's solution is evaporated to and is closely done, wash chicken heart bottle, constant volume with acetonitrile solution；
E. filter membrane after mixing carries out ultra performance liquid chromatography-tandem mass spectrum measurement.
2. the detection method of lincomycin in a kind of cow's milk according to claim 1, it is characterised in that: in the step a
4g sample is weighed, is placed in 50ml centrifuge tube, addition 20ml acetonitrile, whirlpool mixing 30s, the ultrasonic extraction 10min in ice-water bath,
4 DEG C, 8000r/min is centrifuged 5min.
3. the detection method of lincomycin in a kind of cow's milk according to claim 1, it is characterised in that: in the step b
10ml acetonitrile is added, whirlpool mixing 30s, the ultrasonic extraction 10min in ice-water bath, 4 DEG C, 8000r/min is centrifuged 5min.
4. the detection method of lincomycin in a kind of cow's milk according to claim 1, it is characterised in that: in the step c
10ml n-hexane is added in mixing supernatant, whirlpool mixes 1min, and 4 DEG C, 8000r/min is centrifuged 5min.
5. the detection method of lincomycin in a kind of cow's milk according to claim 1, it is characterised in that: in the step d
45 DEG C of rotary evaporations of lower layer's solution are done to close, are settled to 4ml after washing chicken heart bottle with acetonitrile solution.
6. the detection method of lincomycin in a kind of cow's milk according to claim 1, it is characterised in that: in the step d
Acetonitrile solution is the drug solution that acetonitrile is uniformly mixed with use for laboratory level-one water according to volume ratio 1:9.
7. the detection method of lincomycin in a kind of cow's milk according to claim 1, it is characterised in that: in the step e
Cross 0.22 μm of filter membrane.
8. the detection method of lincomycin in a kind of cow's milk according to claim 1, it is characterised in that: chromatographic condition are as follows:
Chromatographic column: 1.8 μm, 2.1*100mm；
Flow velocity: 0.25ml/min；
Sampling volume: 5 μ l；
Column temperature: 40 DEG C.
9. the detection method of lincomycin in a kind of cow's milk according to claim 1, it is characterised in that: mobile phase is washed with degree
The de- time are as follows:
Mobile phase A: volume fraction is 0.1% aqueous formic acid；
Mobile phase B: acetonitrile；
0~0.5min of elution time, Mobile phase B is from 20% linear increase to 85%；
0.5~2.8min of elution time, Mobile phase B keep 85%；
2.8~3.2min of elution time, Mobile phase B are down to 20% from 85%；
3.2~6min of elution time, Mobile phase B keep 20%.
10. the detection method of lincomycin in a kind of cow's milk according to claim 1, it is characterised in that: Mass Spectrometry Conditions are as follows:
Ion source: electric spray ion source；
Scanning mode: cation scanning；
Detection mode: multiple-reaction monitoring；
Capillary voltage: 3.40KV；
Orifice potential: 41V；
Ion source temperature: 120 DEG C；
Desolvation temperature: 360 DEG C；
Desolventizing gas flow: 650L/h；
Taper hole throughput: 50L/h；
Collision gas flow: 0.15ml/min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114088858A (en) * | 2021-11-19 | 2022-02-25 | 江苏省淡水水产研究所 | Detection method of lincosamide antibiotics |
| CN114740122A (en) * | 2022-04-27 | 2022-07-12 | 华南农业大学 | Method for detecting lincomycin in animal food |
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| WO2008127291A2 (en) * | 2006-10-10 | 2008-10-23 | Los Alamos National Security, Llc | Advanced drug development and manufacturing |
| CN101846661A (en) * | 2010-05-24 | 2010-09-29 | 杭州蜂之语蜂业股份有限公司 | Method for simultaneously measuring residual quantities of lincomycin and macrolides in royal jelly |
| CN104764816A (en) * | 2015-03-05 | 2015-07-08 | 中国农业科学院北京畜牧兽医研究所 | UPLC-MS/MS simultaneous flux detection method for multiclass veterinary drug residue in raw fresh milk |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2008127291A2 (en) * | 2006-10-10 | 2008-10-23 | Los Alamos National Security, Llc | Advanced drug development and manufacturing |
| CN101846661A (en) * | 2010-05-24 | 2010-09-29 | 杭州蜂之语蜂业股份有限公司 | Method for simultaneously measuring residual quantities of lincomycin and macrolides in royal jelly |
| CN104764816A (en) * | 2015-03-05 | 2015-07-08 | 中国农业科学院北京畜牧兽医研究所 | UPLC-MS/MS simultaneous flux detection method for multiclass veterinary drug residue in raw fresh milk |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114088858A (en) * | 2021-11-19 | 2022-02-25 | 江苏省淡水水产研究所 | Detection method of lincosamide antibiotics |
| CN114088858B (en) * | 2021-11-19 | 2023-09-01 | 江苏省淡水水产研究所 | Detection method of lincosamide antibiotics |
| CN114740122A (en) * | 2022-04-27 | 2022-07-12 | 华南农业大学 | Method for detecting lincomycin in animal food |
| CN114740122B (en) * | 2022-04-27 | 2023-10-20 | 华南农业大学 | Method for detecting lincomycin in animal food |
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