CN105116063A - Multi-detection method of residual of cephalo-type drugs in milk product - Google Patents
Multi-detection method of residual of cephalo-type drugs in milk product Download PDFInfo
- Publication number
- CN105116063A CN105116063A CN201510403783.2A CN201510403783A CN105116063A CN 105116063 A CN105116063 A CN 105116063A CN 201510403783 A CN201510403783 A CN 201510403783A CN 105116063 A CN105116063 A CN 105116063A
- Authority
- CN
- China
- Prior art keywords
- sample
- detection method
- residual
- joint detection
- formic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
- Cephalosporin Compounds (AREA)
Abstract
The invention belongs to the technical field of detection of residual of drugs in an animal source food, and relates to a method for determining the residual quantity of cephalo-type drugs in a milk product through a high performance liquid chromatograph. The method comprises the steps of sample pre-extraction, standard curve drafting and apparatus detection analysis, the detection method is a multi-detection method carried out by using high performance liquid chromatography, and detected drugs comprise cefoperazone, cefotaxime, ceftriaxone and cephalothin. The cefoperazone detection limit of the method is 0.26mg/Kg, the cefotaxime detection limit of the method is 0.01mg/Kg, the ceftriaxone detection limit of the method is 0.10mg/Kg, and the cephalothin detection limit of the method is 0.07mg/Kg; the method has good linear relationship in an addition concentration range of 1-50mg/kg, and the recovery rate is 90-105%; and the intra-batch relative standard deviation is not greater than 15%, and the inter-batch relative standard deviation is not greater than 20%. The method has the advantages of short analysis time, low detection limit, high precision and multi-detection, and is of great significance to accurately monitor the residual quantity of the cephalo-type drugs in milk.
Description
Technical field
The invention belongs to the detection technique field of animal derived food drug residue, is a kind of method that high performance liquid chromatograph measures cephalosporins medicine residual quantity in dairy product.
Background technology
Along with the fast development of China's animal husbandry, veterinary drug at reduction the livestock and poultry incidence of disease and fatal rate, promotion animal productiong, improve animal meat product quality and improve in efficiency of feed utilization and serve significant effect, become the important support of Modern Animal Husbandry.Cephalosporins (Cephalosporins) belongs to beta-lactam antibiotic, has penicillin resistant enzyme, curative effect is high, toxicity is low, allergic reaction is few, the feature such as has a broad antifungal spectrum, can the Growth and reproduction of effective anti-bacteria.In farming animals cultivation, cephalosporin analog antibiotic is widely used in prevention and the treatment of mastitis for milk cows, the treatment of the bacterial disease of animal urethra, intestines and stomach and respiratory tract etc. and control.But in actual breeding process, lack of standardization due to using method, the drug resistance of animal derived bacterium cause of disease is not only caused to rise, cause the vicious cycle of overdose, and cause the accumulation of the drug residue in livestock products, cause food security hidden danger, bring the serious harms such as allergy, intestinal bacilli illness, drug resistance rising to the mankind.Therefore, the Ministry of Agriculture's clear stipulaties (No. 560, Ministry of Agriculture bulletin): " people such as cefoperazone cures up-to-date antibacterials that clinic control uses for food animal; can produce drug resistance problems; affect animal epidemic control, food security and human health; nullified product authentication code, must not regenerative ratio, operation and use." at present the detection for single medicine mostly is to the detection method of cephalo-type residue of veterinary drug; be not suitable with and current multiple cephalo-type veterinary drug is monitored; therefore, set up a kind of accurate, stable multi-joint detection method significant for the effective monitoring realizing such medicine.
Chinese patent (CN200910085945.7) discloses a kind of enzyme linked immunological kit and the application thereof that detect cephalosporins medicine, by euzymelinked immunosorbent assay (ELISA), cephalo-type residue of veterinary drug is detected, residual quantity can only be judged roughly by light absorption value, antibody preparation process is loaded down with trivial details, detect limit for height, be not easily used as accurate quantification and detect.
Summary of the invention
For solving the problems of the technologies described above, the invention provides the multi-joint detection method that in a kind of quantitative detection dairy product, cephalosporin analog antibiotic is residual, meeting the multi-joint detection demand of the cephalosporin analog antibiotic to herding clinical field forbidding.The present invention detects to be limited to be respectively 0.26mg/kg, 0.01mg/Kg, 0.10mg/kg, 0.07mg/Kg to 4 kinds of cephalosporins medicine such as cefoperazone, CTX, ceftriaxone, cefoxitin; Add concentration range internal linear relation well at 1mg/kg ~ 50mg/kg, the recovery is 90% ~ 105%; Batch interior relative standard deviation≤15% of this method, relative standard deviation≤20% between batch.
Technical scheme of the present invention is a kind of multi-joint detection method detecting cephalosporin analog antibiotic in milk, comprise sample preextraction, Specification Curve of Increasing, instrument detection analytical procedure, described detection method is the multi-joint detection method of one using high performance liquid chromatography to carry out, the medicine simultaneously detected comprises cefoperazone, CTX, ceftriaxone, cefoxitin, specifically comprises the steps:
(1) sample preextraction: take milk sample and be placed in centrifuge tube, add albumen scavenger, centrifugal after ultrasound wave process, Aspirate supernatant is in test tube, and nitrogen dries up, add isopyknic methyl alcohol-0.1% formic acid solution with sample to redissolve, add fat-removal agent and remove fat, vibration, centrifugal, after discarding normal hexane, liquid is transferred in brown bottle after organic membrane filtration, for subsequent use;
Preferably take milk sample and be placed in centrifuge tube, add acetonitrile, ultrasound wave process, the centrifugal 10min of 5000rpm, Aspirate supernatant is in test tube, and nitrogen dries up, and adds and redissolves with sample equal-volume methyl alcohol-0.1% formic acid solution, add normal hexane and remove fat, vibration, the centrifugal 10min of 5000rpm, discards normal hexane, be transferred to after organic membrane filtration in brown bottle, for subsequent use;
(2) drafting of standard solution preparation and typical curve: get standard working solution, carry out different multiples dilution with methyl alcohol-0.1% formic acid solution, drawing standard curve;
Preferably accurately take cefoperazone, CTX, ceftriaxone, each 100mg of cefoxitin standard items respectively, dissolve also constant volume with methyl alcohol-0.1% formic acid and be mixed with single standard solution in 4 brown volumetric flasks of 10mL, draw appropriate single standard solution more respectively and be transferred to precise volume setting in 1 brown volumetric flask of 10mL, be mixed with the hybrid standard product stock solution that concentration is 1mg/mL.With methyl alcohol-0.1% formic acid solution, hybrid standard product solution is diluted through suitable again, be mixed with the hybrid standard product working fluid that concentration is respectively 0.001mg/mL, 0.005mg/mL, 0.010mg/mL, 0.020mg/mL, 0.050mg/mL, high performance liquid chromatograph is adopted to analyze, drawing standard curve, calculates standard regressive method;
(3) step (1) gained sample is entered high performance liquid chromatograph device to detect, testing result and described typical curve are contrasted and obtains testing concentration.
Optimum condition is for adopting Agilent1100 type high performance liquid chromatograph; Agilent (C18,4.6x250,5 μm) ZORBAXEclipsePlus reverse-phase chromatographic column; Mobile phase is A-methyl alcohol, B-0.1% formic acid solution, A: B (volume ratio)=3: 7 ~ 4: 6; Determined wavelength is 254nm; Flow velocity is 1ml/min; Column temperature is 35 DEG C; Sample size is 20 μ l.
Further, the ultrasonic processing method in described step (1) is batch (-type), ultrasound wave process 5 seconds, interval 5 seconds, 60 circulations.
Further, the albumen scavenger in described step (1) is acetonitrile, and the volume ratio of sample liquid and acetonitrile is 1: 3 ~ 1: 4.
Further, the fat-removal agent in described step (1) is normal hexane, and the volume ratio of sample liquid and normal hexane is 2: 1 ~ 2.5: 1.
Further, described methyl alcohol-0.1% formic acid solution, the volume ratio of formic acid and 0.1% formic acid is 3: 7 ~ 4: 6.
Further, the organic filter membrane in described step (1) is that two steps are filtered, and namely first through 0.45 μm of organic membrane filtration, filtered solution is again through 0.22 μm of organic membrane filtration.Can effectively remove interfering material in sample, shorten the processing time, raise the efficiency.
Further, described sample is liquid pure dairy products or milk powder product.
Testing process of the present invention is as follows:
(1) sample pretreatment
Take 5g milk sample, be accurate to 0.01g, sample is placed in centrifuge tube, add 15 ~ 20mL acetonitrile, supersonic oscillations, namely ultrasonic 5 seconds, 5 seconds, interval, 60 circulations, the centrifugal 10min of 5000rpm, gets supernatant, Aspirate supernatant is in test tube, nitrogen dries up, and adds methyl alcohol-0.1% formic acid solution (V/V3: 7 ~ 4: 6) and redissolves, add the grease removal of 2 ~ 2.5mL normal hexane, vibration, the centrifugal 10min of 5000rpm, discards normal hexane, through 0.45 μm and 0.22 μm of laggard high performance liquid chromatograph analysis of membrane filtration first.
(2) testing conditions setting
Condition is for adopting Agilent1100 type high performance liquid chromatograph; Agilent (C18,4.6x250,5 μm) ZORBAXEclipsePlus reverse-phase chromatographic column; Mobile phase is A-methyl alcohol, B-0.1% formic acid solution, A: B (volume ratio)=3: 7 ~ 4: 6; Determined wavelength is 254nm; Flow velocity is 1ml/min; Column temperature is 35 DEG C; Sample size is 20 μ l.
(3) Specification Curve of Increasing
Accurately take cefoperazone, CTX, ceftriaxone, each 100mg of cefoxitin standard items respectively, dissolve also constant volume with methyl alcohol-0.1% formic acid and be mixed with single standard solution in 4 brown volumetric flasks of 10mL, draw appropriate single standard solution more respectively and be transferred to precise volume setting in 1 brown volumetric flask of 10mL, be mixed with the hybrid standard product stock solution that concentration is 1mg/mL.With methyl alcohol-0.1% formic acid solution, hybrid standard product solution is diluted through suitable again, be mixed with the hybrid standard product working fluid that concentration is respectively 0.001mg/mL, 0.005mg/mL, 0.010mg/mL, 0.020mg/mL, 0.050mg/mL, high performance liquid chromatograph is adopted to analyze, drawing standard curve, calculates standard regressive method.
(4) step 1 gained sample is detected through high performance liquid chromatograph device, testing result and described typical curve are contrasted and obtains determinand testing result.
(5) blank assay
Except not adding except sample, all undertaken by said determination condition and step.
(6) result measures
1. qualitative determination
Under same test condition, the ratio of the retention time of target compound and the retention time of target compound in standard working solution in test liquid, deviation is within ± 5%.
2. quantitative measurement
To materials solution and corresponding standard working solution, do multiple spot calibration, by external standard method with peak area quantification.Within the range of linearity that response in standard solution and sample solution all should detect at instrument.
3. result calculates and statement
The residual quantity of cephalosporin analog antibiotic in sample is calculated by formula (a):
In formula:
The residual quantity of cephalosporin analog antibiotic in X-sample, mg/kg;
The concentration of cephalosporin analog antibiotic in C-sample solution, μ g/mL;
The final sample liquid constant volume of V-, mL;
F-extension rate;
M-sample size, g.
Note: result of calculation need deduct blank value.The measurement result arithmetic mean of twice replicate determination represents, retains three position effective digitals.
4. method sensitivity, accuracy and precision
Sensitivity: this method detects to be limited to be respectively 0.26mg/Kg, 0.01mg/Kg, 0.10mg/Kg, 0.07mg/Kg to 4 kinds of cephalosporins medicines such as cefoperazone, CTX, ceftriaxone, cefoxitin.
Accuracy: this method is added in concentration range at 1mg/kg ~ 50mg/kg, and the recovery is 90% ~ 105%.
Precision: batch interior relative standard deviation≤15% of this method, relative standard deviation≤20% between batch.
The present invention's beneficial effect is compared with prior art:
1, the present invention adopts the residual quantity of cephalosporin analog antibiotic in Milk by HPLC, and mobile phase uses methyl alcohol and 0.1% formic acid solution, and proportioning is 3: 7 ~ 4: 6,4 kinds of medicines can be separated completely, ensures sensitivity, avoids interfering with each other.
2, extract uses acetonitrile, effectively can remove protein and partial fat class interfering material; In sample extraction process, adopt normal hexane degrease, effectively can remove fat in sample substrate and wait interfering material.
3, the present invention successively carries out loading pre-treatment by the mode of 0.45 μm and 0.22 μm membrane filtration, can effectively remove interfering material in sample, shortens the processing time, raises the efficiency.
4. this method has been filled up current cephalo-type detection method and has been limitation for single medicine, has enriched multi-joint detection method, has made it have more applicability, be conducive to the effective monitoring of food security.
Accompanying drawing explanation
Fig. 1: the retention time of ceftriaxone;
Fig. 2: the retention time of CTX;
Fig. 3: the retention time of cefoperazone;
Fig. 4: the retention time of cefoxitin;
Fig. 5: the separation spectrogram of cephalosporin analog antibiotic;
Fig. 6: ceftriaxone canonical plotting;
Fig. 7: CTX canonical plotting;
Fig. 8: cefoperazone canonical plotting;
Fig. 9: cefoxitin canonical plotting.
Embodiment
Technology contents of the present invention is described in detail below by embodiment.It will be appreciated by those skilled in the art that following embodiment all for carrying out the description of exemplary to the present invention's scope required for protection, summarize the relative Repeat of each parameter of the present invention with this, therefore it can not be interpreted as one restriction of the present invention.
Dairy product is mainly divided into liquid and solid-state, and therefore, the present invention selects the representational liquid milk of most in milk and milk powder as the embodiment verified.
Embodiment 1:
The present embodiment is the mensuration of cephalosporin analog antibiotic residual quantity in liquid milk, is made up of following steps:
(1) sample pretreatment
Measure liquid milk sample 5mL, be placed in 50mL centrifuge tube, add 15mL acetonitrile, supersonic oscillations (ultrasonic 5 seconds, 5 seconds, interval, 60 circulations), the centrifugal 10min of 5000rpm, Aspirate supernatant is in test tube, and nitrogen dries up, add the redissolution of isopyknic methyl alcohol-0.1% formic acid solution (v/v, 3/7), add the grease removal of 2ml normal hexane, vibration, the centrifugal 10min of 5000rpm, discards normal hexane, through 0.45 μm and 0.22 μm of laggard efficient liquid phase chromatographic analysis of membrane filtration first;
(2) testing conditions setting
Test high-efficient liquid phase chromatogram condition used
Agilent1100 type high performance liquid chromatograph
Agilent (C18,4.6x250,5 μm) ZORBAXEclipsePlus reverse-phase chromatographic column
Mobile phase: A-methyl alcohol, B-0.1% formic acid solution, A: B (volume ratio)=3: 7
Determined wavelength: 254nm
Flow velocity: 1ml/min
Column temperature: 35 DEG C
Sample size: 20 μ l
(3) Specification Curve of Increasing
Accurately take cefoperazone, CTX, ceftriaxone, each 100mg of cefoxitin standard items respectively, dissolve also constant volume with methyl alcohol-0.1% formic acid and be mixed with single standard solution in 4 brown volumetric flasks of 10mL, draw appropriate single standard solution more respectively and be transferred to precise volume setting in 1 brown volumetric flask of 10mL, be mixed with the hybrid standard product stock solution that concentration is 1mg/mL.With methyl alcohol-0.1% formic acid solution, hybrid standard product solution is diluted through suitable again, be mixed with the hybrid standard product working fluid that concentration is respectively 0.001mg/mL, 0.005mg/mL, 0.010mg/mL, 0.020mg/mL, 0.050mg/mL, high performance liquid chromatograph is adopted to analyze, drawing standard curve, calculates standard regressive method;
(4) step 1 gained sample is carried out the detection of high performance liquid chromatograph device, testing result and described typical curve are contrasted and obtains testing concentration.
(5) sample detection and result calculate
1. qualitative determination
Under same test condition, the ratio of the retention time of target compound and the retention time of target compound in standard working solution in test liquid, deviation is within ± 5%.
2. quantitative measurement
To materials solution and corresponding standard working solution, by external standard method with peak area quantification.Within the range of linearity that in standard solution and sample solution, the response of cefoperazone, CTX, ceftriaxone, cefoxitin all should detect at instrument.Standard solution and sample solution feature spectrogram are see Fig. 1.
3. blank assay, quantitative measurement, except not adding except sample, is all undertaken by said determination condition and step.
4. result calculates and statement
Take concentration as horizontal ordinate, peak area is ordinate, and then drawing standard curve carries out analyzing and processing to sample peak, can obtain the concentration treating cephalosporins medicine in sample measuring liquid, calculate the concentration of cephalosporins medicine according to the following formula:
In formula:
The residual quantity of cephalosporin analog antibiotic in X-sample, mg/kg;
The concentration of cephalosporin analog antibiotic in C-sample solution, μ g/mL;
The final sample liquid constant volume of V-, mL;
F-extension rate;
M-sample size, g.
Note: result of calculation need deduct blank value.The measurement result arithmetic mean of twice replicate determination represents, retains three position effective digitals.
(6) result is as shown in table 1
The measurement result of cephalosporins medicine recovery of standard addition and precision in table 1 milk powder
Embodiment 2:
The present embodiment is the mensuration of cephalosporin analog antibiotic residual quantity in solid-state milk, is made up of following steps:
(1) sample pretreatment
Measure solid-state milk sample 1g, add pure water 4ml, mixing is placed in 50mL centrifuge tube, add 20mL acetonitrile, supersonic oscillations (ultrasonic 5 seconds, 5 seconds, interval, 60 circulations), the centrifugal 10min of 5000rpm, Aspirate supernatant is in test tube, and nitrogen dries up, and adds methyl alcohol-0.1% formic acid solution (v/v, 4/6) redissolve, add the grease removal of 2.5ml normal hexane, vibration, the centrifugal 10min of 5000rpm, discard normal hexane, through 0.45 μm and 0.22 μm of laggard efficient liquid phase chromatographic analysis of membrane filtration first;
(2) testing conditions setting
Test high-efficient liquid phase chromatogram condition used
Agilent1100 type high performance liquid chromatograph
Agilent (C18,4.6x250,5 μm) ZORBAXEclipsePlus reverse-phase chromatographic column
Mobile phase: A-methyl alcohol, B-0.1% formic acid solution, A: B (volume ratio)=4: 6
Determined wavelength: 254nm
Flow velocity: 1ml/min
Column temperature: 35 DEG C
Sample size: 20 μ l
(3) Specification Curve of Increasing and testing sample detect
Accurately take cefoperazone, CTX, ceftriaxone, each 100mg of cefoxitin standard items respectively, dissolve also constant volume with methyl alcohol-0.1% formic acid and be mixed with single standard solution in 4 brown volumetric flasks of 10mL, draw appropriate single standard solution more respectively and be transferred to precise volume setting in 1 brown volumetric flask of 10mL, be mixed with the hybrid standard product stock solution that concentration is 1mg/mL.With methyl alcohol-0.1% formic acid solution, hybrid standard product solution is diluted through suitable again, be mixed with the hybrid standard product working fluid that concentration is respectively 0.001mg/mL, 0.005mg/mL, 0.010mg/mL, 0.020mg/mL, 0.050mg/mL, high performance liquid chromatograph is adopted to analyze, drawing standard curve, calculates standard regressive method;
(4) by step 1 sample carry out the detection of high performance liquid chromatograph device, testing result and described typical curve are contrasted and obtain testing concentration.
(5) sample detection and result calculate
1. qualitative determination
Under same test condition, the ratio of the retention time of target compound and the retention time of target compound in standard working solution in test liquid, deviation is within ± 5%.
2. quantitative measurement
To materials solution and corresponding standard working solution, by external standard method with peak area quantification.Within the range of linearity that in standard solution and sample solution, the response of cefoperazone, CTX, ceftriaxone, cefoxitin all should detect at instrument.Standard solution and sample solution feature spectrogram are see Fig. 1.
3. blank assay, quantitative measurement, except not adding except sample, is all undertaken by said determination condition and step.
4. result calculates and statement
Take concentration as horizontal ordinate, peak area is ordinate, and then drawing standard curve carries out analyzing and processing to sample peak, can obtain the concentration treating cephalosporins medicine in sample measuring liquid, calculate the concentration of cephalosporins medicine according to the following formula:
In formula:
The residual quantity of cephalosporin analog antibiotic in X-sample, mg/kg;
The concentration of cephalosporin analog antibiotic in C-sample solution, μ g/mL;
The final sample liquid constant volume of V-, mL;
F-extension rate;
M-sample size, g.
Note: result of calculation need deduct blank value.The measurement result arithmetic mean of twice replicate determination represents, retains three position effective digitals.
(6) result is as shown in table 2
The measurement result of cephalosporins medicine recovery of standard addition and precision in table 2 milk
Claims (9)
1. the multi-joint detection method that in a dairy product, cephalosporins medicine is residual, comprise sample preextraction, Specification Curve of Increasing, instrument detection analytical procedure, it is characterized in that: described detection method is the multi-joint detection method of one using high performance liquid chromatography to carry out, and the medicine simultaneously detected comprises cefoperazone, CTX, ceftriaxone, cefoxitin.
2. the multi-joint detection method that in dairy product as claimed in claim 1, cephalosporins medicine is residual, is characterized in that comprising the following steps:
(1) sample preextraction: take milk sample and be placed in centrifuge tube, add albumen scavenger, centrifugal after ultrasound wave process, Aspirate supernatant is in test tube, and nitrogen dries up, add isopyknic methyl alcohol-0.1% formic acid solution with sample to redissolve, add fat-removal agent and remove fat, vibration, centrifugal, after discarding normal hexane, liquid is transferred in brown bottle after organic membrane filtration, for subsequent use;
(2) drafting of standard solution preparation and typical curve: get standard working solution, carry out different multiples dilution with methyl alcohol-0.1% formic acid solution, drawing standard curve;
(3) step (1) gained sample is entered high performance liquid chromatograph device to detect, testing result and described typical curve are contrasted and obtains testing concentration.
3. the multi-joint detection method that in dairy product as claimed in claim 2, cephalosporins medicine is residual, is characterized in that: the ultrasonic processing method in described step (1) is batch (-type), ultrasound wave process 5 seconds, interval 5 seconds, 60 circulations.
4. the multi-joint detection method that in dairy product as claimed in claim 2, cephalosporins medicine is residual, it is characterized in that: the albumen scavenger in described step (1) is acetonitrile, the volume ratio of sample liquid and acetonitrile is 1: 3 ~ 1: 4.
5. the multi-joint detection method that in dairy product as claimed in claim 2, cephalosporins medicine is residual, it is characterized in that: the fat-removal agent in described step (1) is normal hexane, the volume ratio of sample liquid and normal hexane is 2: 1 ~ 2.5: 1.
6. the multi-joint detection method that in dairy product as claimed in claim 2, cephalosporins medicine is residual, it is characterized in that: described methyl alcohol-0.1% formic acid solution, the volume ratio of formic acid and 0.1% formic acid is 3: 7 ~ 4: 6.
7. the multi-joint detection method that in dairy product as claimed in claim 2, cephalosporins medicine is residual, it is characterized in that: the organic filter membrane in described step (1) is that two steps are filtered, namely first through 0.45 μm of organic membrane filtration, filtered solution is again through 0.22 μm of organic membrane filtration.
8. the multi-joint detection method that in dairy product as claimed in claim 2, cephalosporins medicine is residual, is characterized in that the parameter of the high performance liquid chromatography in described step (2) is as follows: adopt Agilent1100 type high performance liquid chromatograph; Agilent (C18,4.6x250,5 μm) ZORBAXEclipsePlus reverse-phase chromatographic column; Mobile phase is A-methyl alcohol, B-0.1% formic acid solution, volume ratio A: B=3: 7 ~ 4: 6; Determined wavelength is 254nm; Flow velocity is 1ml/min; Column temperature is 35 DEG C; Sample size is 20 μ l.
9. the multi-joint detection method that in dairy product as claimed in claim 1 or 2, cephalosporins medicine is residual, is characterized in that: described sample is liquid pure dairy products or milk powder product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510403783.2A CN105116063B (en) | 2015-07-01 | 2015-07-01 | The multi-joint detection method of cephalosporins medicine residual in a kind of dairy product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510403783.2A CN105116063B (en) | 2015-07-01 | 2015-07-01 | The multi-joint detection method of cephalosporins medicine residual in a kind of dairy product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105116063A true CN105116063A (en) | 2015-12-02 |
| CN105116063B CN105116063B (en) | 2017-03-08 |
Family
ID=54664103
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510403783.2A Active CN105116063B (en) | 2015-07-01 | 2015-07-01 | The multi-joint detection method of cephalosporins medicine residual in a kind of dairy product |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105116063B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106198487A (en) * | 2016-07-05 | 2016-12-07 | 佳木斯大学 | The surface enhanced Raman detection method of Penicillin in Milk medicine |
| CN106501405A (en) * | 2016-11-01 | 2017-03-15 | 中国检验检疫科学研究院 | Cephalosporins residual quick screening method in a kind of animal muscle tissue |
| CN106885854A (en) * | 2017-03-01 | 2017-06-23 | 北京出入境检验检疫局检验检疫技术中心 | The method and its sample-pretreating method of Cephalosporins residual in a kind of detection pluck |
| CN107941951A (en) * | 2017-11-28 | 2018-04-20 | 安徽农业大学 | A kind of method of Quercetin in efficient detection dendrobium candidum |
| CN111141837A (en) * | 2018-11-06 | 2020-05-12 | 江西省农业科学院农产品质量安全与标准研究所 | Method for detecting residual quantity of cefquinome in vegetables |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102419354A (en) * | 2011-09-08 | 2012-04-18 | 宁波检验检疫科学技术研究院 | General rapid detection method for micromolecular poisonous and harmful substances in liquid milk |
-
2015
- 2015-07-01 CN CN201510403783.2A patent/CN105116063B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102419354A (en) * | 2011-09-08 | 2012-04-18 | 宁波检验检疫科学技术研究院 | General rapid detection method for micromolecular poisonous and harmful substances in liquid milk |
Non-Patent Citations (4)
| Title |
|---|
| 李帅鹏 等: "《高效液相色谱-串联质谱法检测牛奶中头孢洛宁残留 》", 《色谱》 * |
| 贾涛: "《液相色谱-串联质谱法检测牛奶中β-内酰胺类药物残留的研究》", 《中国乳业》 * |
| 赵维 等: "《高效液相色谱－串联质谱法测定牛奶中9种青霉素类药物的残留量》", 《浙江大学学报（医学版）》 * |
| 高金兴: "头孢喹肟在牛奶中残留的HPLC检测及消除规律研究", 《中国优秀硕士学位论文》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106198487A (en) * | 2016-07-05 | 2016-12-07 | 佳木斯大学 | The surface enhanced Raman detection method of Penicillin in Milk medicine |
| CN106501405A (en) * | 2016-11-01 | 2017-03-15 | 中国检验检疫科学研究院 | Cephalosporins residual quick screening method in a kind of animal muscle tissue |
| CN106885854A (en) * | 2017-03-01 | 2017-06-23 | 北京出入境检验检疫局检验检疫技术中心 | The method and its sample-pretreating method of Cephalosporins residual in a kind of detection pluck |
| CN106885854B (en) * | 2017-03-01 | 2019-09-24 | 北京出入境检验检疫局检验检疫技术中心 | The remaining method of Cephalosporins and its sample-pretreating method in a kind of detection pluck |
| CN107941951A (en) * | 2017-11-28 | 2018-04-20 | 安徽农业大学 | A kind of method of Quercetin in efficient detection dendrobium candidum |
| CN111141837A (en) * | 2018-11-06 | 2020-05-12 | 江西省农业科学院农产品质量安全与标准研究所 | Method for detecting residual quantity of cefquinome in vegetables |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105116063B (en) | 2017-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105116063A (en) | Multi-detection method of residual of cephalo-type drugs in milk product | |
| CN103940925B (en) | High performance liquid chromatography detects method and the application of sulfa antibiotics fast | |
| CN104280468B (en) | The detection method of horse kind and mule kind derived component in a kind of glue class Chinese medicine and goods thereof | |
| CN103822814A (en) | QuEChERS extraction method for poisonous substance extraction and application of QuEChERS extraction method | |
| CN106226424B (en) | A kind of method of magnetic graphene Solid Phase Extraction combination LC-MS instrument detection meat products veterinary drug residue | |
| Liu et al. | Simultaneous detection and comparative pharmacokinetics of amoxicillin, clavulanic acid and prednisolone in cows’ milk by UPLC–MS/MS | |
| CN101241114A (en) | Animal source food sulfonamide residual medium solid phase dispersion-highly effective liquid phase chromatography determination method | |
| CN103454369A (en) | Method for detecting sodium valproate content of blood through high performance liquid chromatography | |
| CN107102082A (en) | The method of Amitraz and its metabolite residual quantity in liquid chromatography mass/mass spectrometric determination royal jelly | |
| CN102253148A (en) | Method for detecting residues of five kinds of sulfa veterinary medicines in animal-based functional food | |
| CN108519453A (en) | A kind of assay method of 19 kinds of benzimidazoles residues residual quantities based on isotopic dilution-editable multiple-reaction monitoring pattern | |
| CN109142597A (en) | The pre-treating method of Tilmicosin in a kind of detection Swine plasma | |
| Morales-Muñoz et al. | Dynamic ultrasound-assisted extraction of colistin from feeds with on-line pre-column derivatization and liquid chromatography-fluorimetric detection | |
| CN107014915A (en) | The quantitative detecting method of abiraterone in whole blood | |
| CN107957463A (en) | The detection method of lincomycin residual quantity in a kind of soil | |
| CN103776936A (en) | Method for determining content of ivermectin, albendazole sulfoxide and praziquantel in tetramizole | |
| CN106198821B (en) | A kind of method that sulfa antibiotics remain in detection milk | |
| CN109991337A (en) | The method for detecting four class drugs and its metabolin in Eriocheir sinensis crab cream simultaneously | |
| CN108956841A (en) | The detection method of levamisol content in a kind of poultry meat | |
| CN105628808B (en) | Preprocess method and Amoxicillin, the detection method of benzyl penicillin and ospen | |
| CN103940935A (en) | Concentration determining method of arecoline hydrobromide in animal blood plasma | |
| CN106872621B (en) | Method for extracting and purifying residual estrogen in animal sample | |
| CN103616442B (en) | The quantitative detecting method of budesonide isomeride in a kind of animal blood | |
| CN104792899B (en) | Method for detecting residue of multiple quinolones in feed by adopting HPLC-ESI-MS/MS process | |
| CN103439421B (en) | Method for determining content of menbutone injection for veterinary use |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information |
Inventor after: Sun Haixin Inventor after: Xu Na Inventor after: Zhang Hui Inventor after: Sun Pichun Inventor after: Huang Jinfa Inventor before: Sun Haixin Inventor before: Huang Jinfa Inventor before: Zhang Hui Inventor before: Xu Na Inventor before: Sun Pichun |
|
| COR | Change of bibliographic data | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |