CN105510457B - A kind of method for detecting Residue of Antibiotics in Milk - Google Patents
A kind of method for detecting Residue of Antibiotics in Milk Download PDFInfo
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- CN105510457B CN105510457B CN201510863009.XA CN201510863009A CN105510457B CN 105510457 B CN105510457 B CN 105510457B CN 201510863009 A CN201510863009 A CN 201510863009A CN 105510457 B CN105510457 B CN 105510457B
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- 239000008267 milk Substances 0.000 title claims abstract description 29
- 235000013336 milk Nutrition 0.000 title claims abstract description 29
- 210000004080 milk Anatomy 0.000 title claims abstract description 29
- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 15
- 229940088710 antibiotic agent Drugs 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title claims abstract description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 238000001514 detection method Methods 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims abstract description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002414 normal-phase solid-phase extraction Methods 0.000 claims abstract description 5
- 239000008055 phosphate buffer solution Substances 0.000 claims abstract description 5
- 239000003480 eluent Substances 0.000 claims abstract description 4
- 239000000706 filtrate Substances 0.000 claims abstract description 4
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 238000002137 ultrasound extraction Methods 0.000 claims abstract description 4
- 238000010812 external standard method Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 230000003115 biocidal effect Effects 0.000 claims description 23
- -1 hydroxyl metronidazole Chemical compound 0.000 claims description 16
- 229960000282 metronidazole Drugs 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 10
- VAOCPAMSLUNLGC-UHFFFAOYSA-N metronidazole Chemical compound CC1=NC=C([N+]([O-])=O)N1CCO VAOCPAMSLUNLGC-UHFFFAOYSA-N 0.000 claims description 7
- 229960000946 dimetridazole Drugs 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000010828 elution Methods 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 229940060038 chlorine Drugs 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000010355 oscillation Effects 0.000 claims description 3
- 239000008363 phosphate buffer Substances 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000000889 atomisation Methods 0.000 claims description 2
- 238000012790 confirmation Methods 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 238000001819 mass spectrum Methods 0.000 claims description 2
- 238000002552 multiple reaction monitoring Methods 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 238000012360 testing method Methods 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000005119 centrifugation Methods 0.000 abstract description 2
- 235000021393 food security Nutrition 0.000 abstract description 2
- 239000000126 substance Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 150000001720 carbohydrates Chemical class 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 239000012224 working solution Substances 0.000 description 2
- YZEUHQHUFTYLPH-UHFFFAOYSA-N 2-nitroimidazole Chemical compound [O-][N+](=O)C1=NC=CN1 YZEUHQHUFTYLPH-UHFFFAOYSA-N 0.000 description 1
- 241000193830 Bacillus <bacterium> Species 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000283725 Bos Species 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 238000002965 ELISA Methods 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 208000030961 allergic reaction Diseases 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000013365 dairy product Nutrition 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 208000004396 mastitis Diseases 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/027—Liquid chromatography
Abstract
A kind of method for detecting Residue of Antibiotics in Milk, comprises the following steps：(1) milk is placed in centrifuge tube, sequentially adds demulsifier, ethyl acetate and phosphate buffer solution, ultrasonic extraction after centrifugation, obtains liquid to be clean；(2) liquid to be clean is transferred in solid-phase extraction column, purified, collect eluent.Near dry, addition acetonitrile solution is blown to nitrogen in a water bath, after being mixed on turbine mixer, filtrate after miillpore filter is crossed to be measured；(3) determined and confirmed, quantified by external standard method with liquid chromatography tandem mass spectrometry.According to the method for the detection Residue of Antibiotics in Milk of the present invention, the accuracy of testing result can be effectively improved, beneficial ensure is provided for food security.
Description
Technical field
The present invention relates to a kind of method for detecting Residue of Antibiotics in Milk.
Background technology
Residual of the antibiotic in dairy products increasingly causes concern.Except some common inflammation diseases, milk cow is especially
Mastitis is susceptible to suffer from, therefore animal doctor is treated frequently with antibiotic.Due to general antibiotic energy high temperature resistant, existing heating sterilization
The antibiotic residue in milk can not be completely eliminated in technique at all.The milk containing micro antibiotic is drunk for a long time, people can be increased
The drug resistance of Endophytic bacteria, reduces or is completely counterbalanced by the curative effect of antibiotics, in addition, for specific crowd, containing excess
The milk of antibiotic is also possible to that antibiotic allergic reaction can be caused.Therefore, antibiotics leftover detection is carried out to milk to ensureing to eat
Product are significant safely.
At present, mainly there are ELISA and high performance liquid chromatography to the antibiotics leftover detection in milk.These inspections
Survey method is directed to sample pre-treatments step, it is necessary to extract antibiotic from milk.Due to containing protein, fat in milk
The compositions such as fat, carbohydrate, the interface of organic phase and aqueous phase is unclear during extraction, and emulsified state is very serious.Using conventional chemical reagent
Antibiotic composition therein can not be extracted completely, so as to cause the degree of accuracy of testing result not high.
The content of the invention
The purpose of the present invention is that there is provided one kind detection milk for some and some problem present in above-mentioned background technology
The method of middle antibiotic residue.
According to the method for the detection Residue of Antibiotics in Milk of the present invention, comprise the following steps：
(1) 3-5mL milk is measured in centrifuge tube, adds 0.3-0.5g demulsifier, sonic oscillation 15-30 minutes
Afterwards, 10-20mL ethyl acetate is added, after being uniformly dispersed, 10-30mL phosphate buffer solution, 10-20 points of ultrasonic extraction is added
Clock, after centrifugation, is pipetted after 5mL supernatants, plus the mixing of 5mL phosphate buffer solutions, to be clean；
(2) liquid to be clean in step (1) is transferred in solid-phase extraction column, 5mL water, 5mL methanol aqueous solutions is used successively
Elution, is discarded after efflux, decompressing and extracting, is eluted with 5mL methanol, collects eluent.It is blown to closely with nitrogen in 50 DEG C of water-baths
It is dry, 5mL acetonitrile solutions are added, after being mixed on turbine mixer, filtrate after miillpore filter are crossed to be measured；
(3) LC-MS/MS and confirmation, quantified by external standard method are used.
Demulsifier is a kind of surface reactive material, and it can destroy the liquid structure of emulsification shape, each in emulsion to reach
Be separated the purpose come.Demulsifier can be that chemical demulsifier, such as polyoxyethylene polyoxypropylene polyethers or polyoxyethylene gather
Oxypropylene octadecyl alcolol ether；Can also be biological demulsifying agent, such as biological demulsifying agent containing bacillus.Chemical demulsifier cost
Low, long shelf-life.Biological demulsifying agent needs freezen protective, but demulsification is generally better than chemical demulsifier.
In the detection method of the present invention, in sample pre-treatments step, add a certain amount of demulsifier to eliminate emulsification
Phenomenon, promotes the protein in milk, fat, carbohydrate and antibiotic to efficiently separate, and improves the dissolution rate of antibiotic in sample.Again
Coordinate with suitable extractant, under suitable pH value condition, extract the antibiotic in milk.So as to ensure that on source
The accuracy of final detection result.
According to the method for the detection Residue of Antibiotics in Milk of the present invention, the accuracy of testing result can be effectively improved,
Beneficial ensure is provided for food security.
Embodiment
The method of the detection Residue of Antibiotics in Milk of the present invention is described in detail below by specific embodiment.This area skill
Art personnel should be appreciated that the embodiments described below is only the exemplary illustration to the present invention, any not for being made to it
Limitation.
, as sample, to detect its 5 kinds of nitre through the milk of preliminary examination (such as Antimicrobial test paper method) containing antibiotic
Base imidazoles antibiotic medicine (hydroxyl metronidazole, 2- metronidazoles, hydroxyl Dimetridazole, metronidazole, chlorine metronidazole) is residual
The concrete content stayed, to introduce the implementation process and effect of the present invention.
1. it is prepared by sample liquid A
1.1 extraction step
5mL milk is taken in centrifuge tube, 0.3g polyoxyethylene polyoxypropylene polyethers, sonic oscillation 30 minutes is added
Afterwards, 20mL ethyl acetate is added, after being uniformly dispersed, 30mL phosphate buffer solution, ultrasonic extraction 20 minutes, warp is added
After 7000r/min is centrifuged 10 minutes, pipette after 5mL supernatants, plus the mixing of 5mL phosphate buffer solutions, it is to be clean；
1.2 purification step
Liquid to be clean in step 1.1 is transferred in HLB solid-phase extraction columns, 5mL water, 5mL methanol aqueous solutions are used successively
Elution, is discarded after efflux, decompressing and extracting, is eluted with 5mL methanol, collects eluent.It is blown to closely with nitrogen in 50 DEG C of water-baths
It is dry, 5.0mL acetonitrile solutions are added, after being mixed on turbine mixer, filtrate after 0.22 micron of miillpore filter are crossed to be measured.
In above-mentioned steps, phosphate buffer solution concentration is 0.1mol/L, and preparation process is：Dissolve 12.2g biphosphates
Sodium adjusts pH value to 8.0 with 0.1mol/L sodium hydroxide solutions, is finally diluted with water to 1L in 950mL water.Methanol aqueous solution
The volume ratio of middle methanol and water is 3:7.Acetonitrile and water volume ratio are 2 in acetonitrile solution:8.
2. it is prepared by sample liquid B
In order to contrast, polyoxyethylene polyoxypropylene polyethers is added without in above-mentioned preparation sample liquid A step 1.1, it is other
Step is completely identical with sample liquid A.
3. it is prepared by titer
It is accurate to weigh appropriate each standard substance (hydroxyl metronidazole, 2- metronidazoles, hydroxyl Dimetridazole, metronidazole, chlorine
Metronidazole) it is respectively placed in 50mL volumetric flasks, with methanol constant volume to scale, it is configured to the storing solution that concentration is 10mg/L.
Storing solution diluted step by step with acetonitrile solution obtain hydroxyl metronidazole, 2- metronidazoles, hydroxyl Dimetridazole,
Metronidazole, chloromethane nitre imidazole concentration are 10 μ g/L, 20 μ g/L, 50 μ g/L, 100 μ g/L, 200 μ g/L, 400 μ g/L, 800 μ g/L
Serial hybrid standard working solution.
4. liquid chromatography-mass spectrography is detected
The condition of work of 4.1 liquid chromatograies
A) chromatographic column：C18 posts, 100mm × 2.1mm (i.d.), 5 μm.
B) mobile phase：A：Acetonitrile, B：0.2% formic acid solution, gradient elution, gradient condition is shown in Table 1.
C) column temperature：30℃.
D) sample size：10μL.
The gradient elution program table of table 1
4.2 tandem mass spectrum conditions of work
A) mode is ionized：Electron spray ionisation, positive ion mode；
B) spray voltage：3.0kV；
C) atomization temperature：300℃；
D) capillary temperature：350℃；
E) sheath atmospheric pressure：50Arb (1Arb=1psi)；
F) assist gas pressure power：20Arb (1Arb=0.3L/min)；
G) collision gas, sheath gas and auxiliary gas：Argon gas (99.999%)；
H) scan pattern：Multiple-reaction monitoring (MRM) pattern, the mass spectrometry parameters of 5 kinds of nitroimidazole antibiotics are shown in Table 2.
The mass spectrometry parameters of table 2
* quota ion
4.3 determination step
First hybrid standard working solution is detected from low to high by concentration, mass concentration made with quota ion peak area
Figure, makes standard curve regression equation.
Sample liquid is detected again, obtained ion peak areas obtains the concentration of each antibiotic with standard curve control.
Sample liquid detection number of times is 5 times, is averaged as result.
If the response for having component in sample liquid is above standard the range of linearity of curve, sample introduction is determined again after dilution.
Test result is as shown in table 3.
5 kinds of nitro miaows in the sample liquid of table 3Class antibiotic content testing result
The above results show that the various antibiotic contents detected in sample liquid A are all higher than the content in sample liquid B, special
Not for the hydroxyl metronidazole and hydroxyl Dimetridazole that are not detected in sample B, but small content is detected in sample liquid A.
So as to show, in the extraction process of sample liquid, add a certain amount of demulsifier and carry out demulsification processing, the recovery rate energy of antibiotic
More than 10% is enough improved, the degree of accuracy of Residue of Antibiotics in Milk detection is substantially increased.
Above-described embodiment is detected using the milk for containing antibiotic through preliminary examination as sample, only for more fully understanding
The present invention.It should be appreciated by those skilled in the art that the detection method of the present invention goes for all kinds of oxen without preliminary examination
Milk.Detection project is also not necessarily limited to nitro miaowThe antibiotic of class antibiotic or the other species of detection.
Claims (2)
1. a kind of method for detecting Residue of Antibiotics in Milk, comprises the following steps：
(1) 3-5mL milk is measured in centrifuge tube, adds 0.3-0.5g demulsifier, sonic oscillation is after 15-30 minutes, plus
Enter 10-20mL ethyl acetate, after being uniformly dispersed, addition 10-30mL phosphate buffer solution, ultrasonic extraction 10-20 minutes, from
After the heart, pipette after 5mL supernatants, plus the mixing of 5mL phosphate buffer solutions, it is to be clean；
(2) liquid to be clean in step (1) is transferred in solid-phase extraction column, 5mL water is used successively, 5mL methanol aqueous solutions are eluted,
Discard after efflux, decompressing and extracting, eluted with 5mL methanol, collect eluent；It is blown to and is closely done with nitrogen in 50 DEG C of water-baths, plus
Enter 5mL acetonitrile solutions, after being mixed on turbine mixer, cross filtrate after miillpore filter to be measured；
(3) LC-MS/MS and confirmation, quantified by external standard method are used；
The demulsifier is polyoxyethylene polyoxypropylene polyethers or polyoxyethylene polyoxypropylene octadecyl alcolol ether；
The solid-phase extraction column is HLB extraction columns；
The antibiotic is hydroxyl metronidazole, 2- metronidazoles, hydroxyl Dimetridazole, metronidazole, chlorine metronidazole；
The Liquid Chromatography-Tandem Mass Spectrometry is：
The condition of work of liquid chromatogram：
A) chromatographic column：C18 posts, 100mm × 2.1mm (i.d.), 5 μm；
B) mobile phase：A：Acetonitrile, B：0.2% formic acid solution, gradient elution,
Gradient elution program：
Time 0.0min：A 10%, B 90%, flow velocity 0.30mL/min；
Time 2.0min：A 20%, B 80%, flow velocity 0.30mL/min；
Time 4.0min：A 30%, B 70%, flow velocity 0.30mL/min；
Time 7.0min：A 40%, B 60%, flow velocity 0.30mL/min；
Time 10.1min：A 95%, B 5%, flow velocity 0.30mL/min；
Time 11.0min：A 10%, B 90%, flow velocity 0.30mL/min；
Time 18.0min：A 10%, B 90%, flow velocity 0.30mL/min；
C) column temperature：30℃；
D) sample size：10μL；
Tandem mass spectrum condition of work：
A) mode is ionized：Electron spray ionisation, positive ion mode；
B) spray voltage：3.0kV；
C) atomization temperature：300℃；
D) capillary temperature：350℃；
E) sheath atmospheric pressure：50Arb；
F) assist gas pressure power：20Arb；
G) collision gas, sheath gas and auxiliary gas：99.999% argon gas；
H) scan pattern：Multiple-reaction monitoring pattern.
2. the method for detection Residue of Antibiotics in Milk according to claim 1, the miillpore filter specification is 0.22 μm.
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN106645509A (en) * | 2016-11-09 | 2017-05-10 | 无锡艾科瑞思产品设计与研究有限公司 | Detection method for antibiotic residue in milk |
| 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 |
| CN109406249B (en) * | 2018-11-30 | 2022-10-14 | 江苏美正生物科技有限公司 | Pretreatment method for food safety drug residue detection |
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|---|---|---|---|---|
| EP1239280A2 (en) * | 2001-02-26 | 2002-09-11 | Pfizer Products Inc. | ElogDoct:A tool for lipophilicity determination in drug discovery basic and neutral compounds |
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| JP4563764B2 (en) * | 2004-10-01 | 2010-10-13 | 丸善製薬株式会社 | Peptide quantification method |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1239280A2 (en) * | 2001-02-26 | 2002-09-11 | Pfizer Products Inc. | ElogDoct:A tool for lipophilicity determination in drug discovery basic and neutral compounds |
Non-Patent Citations (4)
| Title |
|---|
| Confirmatory method for the determination of nitroimidazoles in milk by liquid chromatography - tandem mass spectrometry;Kamila Mitrowska et al.;《Bull Vet Inst Pulawy》;20141231;第58卷;第581-587页 * |
| Determination of four nitroimidazole residues in poultry meat by liquid chromatography–mass spectrometry;Dominique Hurtaud-Pessel et al.;《Journal of Chromatography A》;20001231;第882卷;第89-98页 * |
| 液相色谱一四极杆／离子阱质谱快速测定蜂蜜中痕量硝基咪唑类药物及其代谢物残留;张鸿伟等;《分析测试学报》;20120731;第31卷(第7期);第763-770页 * |
| 蛋、奶中甲硝唑残留检测的高效液相色谱法研究;艾霞等;《华中农业大学》;20060630;第25卷(第3期);第266-269页 * |
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