CN104990996A - Method for detecting antibiotic residues in milk, and application thereof - Google Patents
Method for detecting antibiotic residues in milk, and application thereof Download PDFInfo
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Abstract
The invention relates to a method for detecting antibiotic residues in milk, and an application thereof, and belongs to the field of food safety. The invention discloses an online solid phase extraction-high performance liquid chromatography-mass spectrometry detection method in order to solve the detection problem of antibiotic residues in milk. The method allows five types of 33 veterinary drug residues comprising sulfanilamides, quinolones, beta-lactams, tetracyclines and chloramphenicols in the milk to be simultaneously detected. Influences of various factors on the reservation and selectivity of various antibiotics are optimized, so the method has the characteristics of high sensitivity, high recovery rate, high stability and high precision. The detected antibiotics can be qualitatively and quantitatively determined according to the reservation time and accurate mass numbers. The amounts of samples and reagents required and used in the method are small, the detection speed is fast, all operation processes are completed within 15.5min, and cost reduction and operating risk mitigation of dairy product processing enterprises are guaranteed.
Description
Technical field
The present invention relates to monitoring method and the application thereof of Residue of Antibiotics in Milk, belong to field of food safety, particularly field of detection of food safety.
Background technology
All nutriments that the milk needed by human body be rich in except dietary fiber is wanted, the height of its nutrition is that other foods are irreplaceable.Fresh milk and dairy produce have become the important component part in people (especially old man and children) life food.In recent years, along with developing rapidly of China's livestock breeding industry, milk yield increases substantially, in order to diseases such as prophylactic generation and treatment mammitises, culturist can add containing the antibiotic feed addictive of certain proportion in ox feed and in potable water, but, will inevitably cause in milk antibiotic residual like this.If drink containing antibiotic milk for a long time, the microbiotic in milk enters human body by food chain, equals the microbiotic of long-term taking low dose beyond doubt.Allergic reaction can be caused after the people of microbiotic allergic constitution being taken to the milk of residual antibiotic.Normal drinking person, can cause some the conditionality pathogenic bacteria in body easily to produce drug resistance, be difficult to prove effective again once ill with antibiotic therapy of the same race.Antibiotic residue not only harm humans is healthy, also affects the quality of milk simultaneously.The food law of the World Food Programme (FAO), the World Health Organization (WHO) (WHO) has made detailed regulation to the most high residue amount of microbiotic in milk.The Ministry of Agriculture of China calendar year 2001 has issued and implemented " pollution-free food Fresh Milk industry standard ".Therefore, set up a kind of, simply, the method that detects multiple antibiotic residues in milk quickly and efficiently have to be necessary.
Due to the medicine of sulfamido, quinolones, beta-lactam, Tetracyclines, chloromycetin totally 5 large classes 33 kinds of veterinary drugs, its chemical molecular structure and chemical property differ greatly, there is certain difficulty to detecting while multiple antibiotic residues in milk simultaneously, also there is no bibliographical information at present.For Residue of Antibiotics in Milk analysis, the pretreatment technologies such as solid phase extraction techniques, solid phase micro-extraction technique and matrix solid phase dispersion have been applied in sample pre-treatments step, with solve sample analysis test in matrix interference problem.Wherein, being most widely used of solid phase extraction techniques, but be applied in the pre-treatment that Residue of Antibiotics in Milk detects, but ubiquity sample handling processes be complicated, toxic reagent contact is many for solid phase extraction techniques, consumptive material consumption greatly, need that extra nitrogen blows, poor reproducibility and the automatically problem such as online cannot be realized.The particularly medicine such as Tetracyclines, because it is combined with protein or mineral matter, is formed in conjunction with state, has therefore more increased the weight of the antibiotic detection difficulty of Residues in Milk.
Summary of the invention
The object of the invention is to the test problems for current Residue of Antibiotics in Milk, there is provided one simply, detection method fast, thus sulfamido in milk, quinolones, beta-lactam, Tetracyclines, chloromycetin totally five large classes 33 kinds of residues of veterinary drug can be detected simultaneously.
The detection method of Residue of Antibiotics in Milk disclosed in this invention is on-line solid phase extraction-high performance liquid chromatography-mass spectrometry detection method.
Wherein: on-line solid phase extraction adopts C18 post or HLB post, the rinse procedures of described on-line solid phase extraction comprises the following steps, first successively by methanol-water-buffer solution activation, specific procedure is, methyl alcohol is with the drip washing speed drip washing 0.2min of 5mL/min, water is with the drip washing speed drip washing 0.4min of 5mL/min, buffer solution is with the drip washing speed drip washing 0.6min of 5mL/min, then by milk sample loading to be measured, specific procedure is, water is with the drip washing speed drip washing 1.6min of 0.5mL/min, methyl alcohol is utilized to carry out wash-out afterwards, specific procedure is, methyl alcohol is with the drip washing speed drip washing 2.6min of 0.15mL/min, last priority is rinsed by water-methyl alcohol, specific procedure is, water is with the drip washing speed drip washing 2.8min of 5mL/min, then methyl alcohol is with the drip washing speed drip washing 3.0min of 5mL/min,
Here the buffer solution that we use is phosphate, any one in acetate, citrate.
Described high performance liquid chromatography adopts C18 analytical column, column temperature is 30 °, adopt formic acid water/methyl alcohol as eluent, the mode of gradient elution is utilized to carry out wash-out, gradient is respectively 95:5,75:25,5:95,95:5 by volume, and each gradient elution time is respectively 2.5min, 3.5min, 4.0min, 2.5min.
Described mass spectrum adopts ionization electron spray, electric spray ion source is HESI-II, capillary temperature is 350 DEG C, sheath gas velocity 50L/min, assisted gas flow velocity 6L/min, sweep gas flow velocity 3L/min, spray voltage is 3KV, and lens voltage is 50V, and image data or negative ions switch image data simultaneously respectively to adopt positive ion and negative ion mode, the resolution R=70000 of one-level full scan, sweep limit 100 ~ 1000m/z.
Further, the method for making that we also disclosed described milk sample to be measured is: milk to be measured mixes with protein precipitant by (1), buffer solution is added in the solution after mixing, regulate pH to 3.5 ~ 7.5, (2) potpourri step (1) obtained is centrifugal, filtration, collect supernatant, be milk sample to be measured.Wherein preferably following any one or several optimum condition,
The addition of described protein precipitant is 0.2 ~ 5 times that milk to be measured adds weight,
Described protein precipitant be preferably in aqueous zinc acetate solution, acetic acid lead solution, ammonium acetate solution, solution of trichloroacetic acid, methyl alcohol, acetonitrile or glacial acetic acid aqueous solution any one, wherein glacial acetic acid aqueous solution is preferably the glacial acetic acid aqueous solution of 1% ~ 10%.
The addition of described buffer solution is 0.1 ~ 0.5 times that milk to be measured adds weight;
Described buffer solution is any one in aqueous phosphatic, acetate aqueous solution or saline citrate; The concentration range of buffer solution is 0.5 ~ 5.0mol/L.
Described centrifugal condition is 600 ~ 3000r/min, and centrifugation time is 3 ~ 8min.
Before sample introduction, need to carry out filtration treatment to supernatant, preferably adopt filter membrane to be here average pore size be the filter membrane of 0.45 μm.
Further, we also disclosed the application of detection method in milk antibiotic residue quantitatively detects of aforementioned Residue of Antibiotics in Milk.
When quantitatively detecting, needing with different microbiotic standard items production standard liquid, adopting internal standard method drawing standard working curve.The horizontal ordinate of its standard curve is concentration of standard solution, and ordinate is standard solution peak area and internal standard area ratio.
Finally, whether the application of the detection method that we also disclosed aforementioned Residue of Antibiotics in Milk in the monitoring of milk antibiotic residue, by containing certain or certain several microbiotic in the chromatographic peak retention time of comparison standard items and sample and accurate mass number deviation determination sample.
The on-line solid phase extraction technology that this experiment adopts is a kind of full automatic on-line sample preparation mode, by optimizing solid phase extraction concentration condition, analysis chromatographic column, mobile phase is on the reservation of Multiple Classes of Antibiotics and optionally affect, and realizes the quick detection of Multiple Classes of Antibiotics in milk substrate first.Online connection can avoid the analysis thing loss brought because of complicated pretreatment process, reduces operator because of solvent volatilization and the contact of toxic solvent, improves detection efficiency and flux, have broad application prospects.
. sample size required for the present invention and reagent dosage few, only need 10-100 μ l.Inventive samples pre-treatment is simple, and milk sample gets final product direct injected after only needing protein precipitation to add buffer solution adjustment pH, the steps such as nitrogen when eliminating conventional solid extraction process blows, concentrate.Inventive samples is short for analysis time, and detection speed is fast, and a sample only needs 15.5min.The present invention is strong to the selectivity of target compound, and antijamming capability is strong, can exclusive PCR component and extract target substance from complex matrices.Measure under the on-line solid phase extraction that the present invention sets up, chromatographic mass spectrometry condition, within the scope of experimental concentration, correlation coefficient r can reach more than 0.999, the recovery between 70.3-125.8%, when the relative standard deviation of in a few days testing with a few day to day precision is all less than 5.0%.The Dairy Processing enterprise that is detected as fast of Residue of Antibiotics in Milk produces and reduces costs, alleviates operational risk and provide guarantee.
Accompanying drawing explanation
Fig. 1 is the mass spectrogram in embodiment 1 in milk sample.
Embodiment
The detection of embodiment 1. pasteurization Ruzhong multiple antibiotic residues
(1) the preparation of sample
Accurately take milk sample 1.00g (± 0.01g) in centrifuge tube, add the acetic acid zinc solution that 0.5ml concentration is 1mol/L, after vortex mixing, add 1mol/L phosphate buffer solution 1ml again, the pH value controlling solution is 4.5, after centrifugal filtration, the filter membrane crossing 0.45 μm, in sample injection bottle, measures for on-line solid phase extraction-high resolution liquid chromatography-mass spectrometer.
(2) the gradient conditions of on-line solid phase extraction post is as shown in table 1, and required solid-phase extraction column is C18 or HLB post.
The gradient condition of table 1 on-line solid phase extraction
(3) the chromatographic separation condition of high performance liquid chromatography-high resolution mass spectrometer is as shown in table 2, and analytical column filler used is C18, column temperature, is 30 DEG C.
Table 2 chromatographic condition
| Time (min) | Flow velocity (mL/min) | Formic acid water (%) | Methyl alcohol (%) |
| 0 | 0.70 | 95 | 5 |
| 2 | 0.70 | 95 | 5 |
| 2.5 | 0.70 | 75 | 25 |
| 6 | 0.70 | 5 | 95 |
| 9.5 | 0.70 | 5 | 95 |
| 10 | 0.70 | 95 | 5 |
| 12.5 | 0.70 | 95 | 5 |
(4) Mass Spectrometry Conditions
Heatable electric spray ion source (HESI-II); Capillary temperature is 350 DEG C, sheath gas (N
2) flow velocity 50L/min, assisted gas (N
2) flow velocity 6L/min, sweep gas (N
2) flow velocity 3L/min; Spray voltage is 3KV, and lens voltage is 50V; Image data or negative ions switch image data, the resolution R=70000 of one-level full scan, sweep limit: 100-1000m/z simultaneously respectively to adopt positive ion and negative ion mode.
Thus obtain microbiotic mass spectrogram in milk sample as shown in Figure 1.
By Fig. 1, we see pasteurization Ruzhong to be detected, containing sulfapryidine, sulphadiazine, sulfamethoxazole, sulphathiazole and sulfamethyldiazine.
Embodiment 2
On the basis of embodiment 1, further in the present embodiment, preparation mass concentration is 10,50,75,100.0, the standard working solution of 200.0ng/mL, with standard solution peak area and internal standard area ratio for ordinate, solution concentration (ng/ml) is horizontal ordinate, drawing standard working curve.All compounds are good in 10 ~ 200ng/mL scope internal linear relation, and related coefficient (r) is greater than 0.99.With standard working curve, sample is carried out quantitatively.The response of sample solution Chinese traditional medicine all should in the range of linearity of Instrument measuring.
Whether there is certain microbiotic in judgement sample, following condition need be met: the retention time of chromatographic peak that this sample occurs differ with standard items retention time be no more than ± 2.5%; The deviation of the accurate mass number of sample and standard items is less than 5 × 10
-6, be then defined as in sample containing this medicine.The wherein accurate mass number reference table 3 of standard items retention time and standard items.
The Chinese and English title of table 3 antibiotic medicine, retention time and mass spectrum accurate mass number (positive ion)
The detection of multiple antibiotic residues in embodiment 3. organic milk
Take pasteurized milk as negative controls, detect the antibiotic residue in pasteurized milk and organic milk respectively.
In accordance with the following methods, respectively pasteurized milk and organic milk are processed.
Accurately take milk sample 1.00g (± 0.01g) in centrifuge tube, add the acetic acid zinc solution that 0.5mL concentration is 1mol/L, after vortex mixing, add 1mol/L phosphate buffer solution 1mL again, the pH value controlling solution is 4.5, after centrifugal filtration, the filter membrane crossing 0.45 μm, in sample injection bottle, measures for on-line solid phase extraction-high resolution liquid chromatography-mass spectrometer.On-line solid phase extraction and analysis chromatographic condition are as shown in table 2 and table 3.To analyze the recovery of negative sample pasteurized milk and organic milk as shown in table 4.
The recovery of standard addition (Pitch-based sphere is 10 μ g/kg) of multiple antibiotic residues in the typical organic milk of table 4 and pasteurized milk negative sample
According to upper table, we can find out, all medicines recovery scope in pasteurized milk and organic milk is 69.7-124.1, can meet the demand that our routine analysis detects.
Claims (8)
1. the detection method of Residue of Antibiotics in Milk, is characterized in that, described detection mode is on-line solid phase extraction-high performance liquid chromatography-mass spectrometry detection method.
2. the detection method of Residue of Antibiotics in Milk according to claim 1, it is characterized in that, described on-line solid phase extraction adopts C18 post or HLB post, the rinse procedures of described on-line solid phase extraction comprises the following steps, first successively by methanol-water-buffer solution activation, specific procedure is, methyl alcohol is with the drip washing speed drip washing 0.2min of 5mL/min, water is with the drip washing speed drip washing 0.4min of 5mL/min, buffer solution is with the drip washing speed drip washing 0.6min of 5mL/min, then by milk sample loading to be measured, specific procedure is, water is with the drip washing speed drip washing 1.6min of 0.5mL/min, methyl alcohol is utilized to carry out wash-out afterwards, specific procedure is, methyl alcohol is with the drip washing speed drip washing 2.6min of 0.15mL/min, last priority is rinsed by water-methyl alcohol, specific procedure is, water is with the drip washing speed drip washing 2.8min of 5mL/min, then methyl alcohol is with the drip washing speed drip washing 3.0min of 5mL/min,
Wherein said buffer solution is any one in phosphate, acetate, citrate.
3. the detection method of Residue of Antibiotics in Milk according to claim 1, it is characterized in that, described high performance liquid chromatography adopts C18 analytical column, column temperature is 30 °, adopt formic acid water/methyl alcohol as eluent, utilize the mode of gradient elution to carry out wash-out, gradient is respectively 95:5,75:25,5:95,95:5 by volume, and each gradient elution time is respectively 2.5min, 3.5min, 4.0min, 2.5min.
4. the detection method of Residue of Antibiotics in Milk according to claim 1, it is characterized in that, described mass spectrum adopts ionization electron spray, electric spray ion source is HESI-II, capillary temperature is 350 DEG C, sheath gas velocity 50L/min, assisted gas flow velocity 6L/min, sweep gas flow velocity 3L/min, spray voltage is 3KV, and lens voltage is 50V, and image data or negative ions switch image data simultaneously respectively to adopt positive ion and negative ion mode, the resolution R=70000 of one-level full scan, sweep limit 100 ~ 1000m/z.
5. the detection method of Residue of Antibiotics in Milk according to claim 2, it is characterized in that, the method for making of described milk sample to be measured is: milk to be measured mixes with protein precipitant by (1), buffer solution is added in the solution after mixing, regulate pH to 3.5 ~ 7.5, (2) potpourri step (1) obtained is centrifugal, filtration, collects supernatant, is milk sample to be measured.
6. the detection method of Residue of Antibiotics in Milk according to claim 5, is characterized in that, possesses following any one or several optimum condition,
The addition of described protein precipitant is 0.2 ~ 5 times that milk to be measured adds weight,
Described protein precipitant be preferably in aqueous zinc acetate solution, acetic acid lead solution, ammonium acetate solution, solution of trichloroacetic acid, methyl alcohol, acetonitrile or glacial acetic acid aqueous solution any one,
The addition of described buffer solution is 0.1 ~ 0.5 times that milk to be measured adds weight;
Described buffer solution is any one in aqueous phosphatic, acetate aqueous solution or saline citrate;
Described centrifugal condition is 600 ~ 3000r/min, and centrifugation time is 3 ~ 8min.
7. the application of detection method in milk antibiotic residue quantitatively detects of arbitrary Residue of Antibiotics in Milk in claim 1 ~ 6.
8. in claim 1 ~ 6 arbitrary Residue of Antibiotics in Milk detection method milk antibiotic residue monitoring in application.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106198821A (en) * | 2016-08-29 | 2016-12-07 | 郑州点石生物技术有限公司 | A kind of method detecting the residual of sulfa antibiotics in milk |
| CN106324155A (en) * | 2016-11-02 | 2017-01-11 | 百奥森（江苏）食品安全科技有限公司 | Detection method for antibiotic residue in milk |
| CN106442755A (en) * | 2016-08-29 | 2017-02-22 | 郑州点石生物技术有限公司 | Detection method of sulfonamide antibiotic residues in milk |
| CN106596780A (en) * | 2016-12-21 | 2017-04-26 | 南京大学 | Method for detecting contents of various antibiotics in water by combined use of high pressure liquid chromatography and mass spectrum |
| CN107703248A (en) * | 2017-11-20 | 2018-02-16 | 山东五洲检测有限公司 | A kind of method of antibiotic content in detection milk |
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| CN112051345A (en) * | 2020-09-17 | 2020-12-08 | 河南省奶牛生产性能测定有限公司 | High performance liquid chromatography detection method for sulfonamides in raw fresh milk |
| CN113155991A (en) * | 2021-03-03 | 2021-07-23 | 江南大学 | Method for rapidly determining sulfonamide antibiotics in water by full-automatic online extraction ultra-high performance liquid chromatography-tandem mass spectrometry |
| CN115372524A (en) * | 2022-09-30 | 2022-11-22 | 重庆市天友乳业股份有限公司 | Method for extracting chloramphenicol residues in cow milk and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101290306A (en) * | 2008-06-18 | 2008-10-22 | 内蒙古蒙牛乳业（集团）股份有限公司 | Milk and milk product tetracycline antibiotic residual quantity checking method |
| CN201876442U (en) * | 2010-11-11 | 2011-06-22 | 复旦大学 | Seamless connection device for detecting antibiotics in milk on line |
| CN102269747A (en) * | 2011-05-03 | 2011-12-07 | 东华大学 | Method for simultaneously detecting various antibiotics quantitatively at one time |
| CN104597175A (en) * | 2013-10-30 | 2015-05-06 | 内蒙古蒙牛乳业（集团）股份有限公司 | Sample pretreatment method for detecting kanamycins in milk and detection method for kanamycins in milk |
-
2015
- 2015-05-19 CN CN201510255542.8A patent/CN104990996B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101290306A (en) * | 2008-06-18 | 2008-10-22 | 内蒙古蒙牛乳业（集团）股份有限公司 | Milk and milk product tetracycline antibiotic residual quantity checking method |
| CN201876442U (en) * | 2010-11-11 | 2011-06-22 | 复旦大学 | Seamless connection device for detecting antibiotics in milk on line |
| CN102269747A (en) * | 2011-05-03 | 2011-12-07 | 东华大学 | Method for simultaneously detecting various antibiotics quantitatively at one time |
| CN104597175A (en) * | 2013-10-30 | 2015-05-06 | 内蒙古蒙牛乳业（集团）股份有限公司 | Sample pretreatment method for detecting kanamycins in milk and detection method for kanamycins in milk |
Non-Patent Citations (5)
| Title |
|---|
| D.A. BOHM ET AL.: "Multi-method for the determination of antibiotics of different substance groups in milk and validation in accordance with Commission Decision 2002/657/EC", 《JOURNAL OF CHROMATOGRAPHY A》 * |
| LINA KANTIANI ET AL.: "Fully Automated Analysis of β-Lactams in Bovine Milk by Online Solid Phase Extraction-Liquid Chromatography-Electrospray-Tandem Mass Spectrometry", 《ANAL. CHEM.》 * |
| 张尹 等: "超声辅助萃取-高效液相色谱法测定牛奶中9种β-内酰胺抗生素残留", 《云南大学学报（自然科学版）》 * |
| 顾欣 等: "阳离子交换在线固相萃取/液相色谱-串联质谱法检测牛奶中14种磺胺药物残留", 《分析化学》 * |
| 黄百芬 等: "超高效液相色谱-串联质谱法同时测定牛奶中19种β -内酰胺类抗生素", 《中国卫生检验杂志》 * |
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| CN107703248A (en) * | 2017-11-20 | 2018-02-16 | 山东五洲检测有限公司 | A kind of method of antibiotic content in detection milk |
| CN108732273B (en) * | 2018-06-06 | 2020-10-16 | 山东省分析测试中心 | Method for analyzing trace sulfonamide antibiotics in food and drinking water |
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| CN109655438A (en) * | 2019-01-09 | 2019-04-19 | 遵义医学院 | The detection method of content of Marbofloxacin in water sample |
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