CN101315351A - HPLC-ESI-MS/MS measuring method for simultaneously detecting 19 kinds of carbostyril medicaments - Google Patents
HPLC-ESI-MS/MS measuring method for simultaneously detecting 19 kinds of carbostyril medicaments Download PDFInfo
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Abstract
A detection method for detecting HPLC-ESI-MS/MS of 19 species of quinolone drugs simultaneously belongs to the antibiotic drug analysis technology field. The detection method comprises three steps: sample treatment, liquid-phase separation and mass spectrometric detection, wherein the 19 species of quinolone antibiotics in a tissue fluid is subjected to positive ion MRM scan; norfloxacin-D5 is taken as the internal standard; C18 chromatographic columns are adopted for separation; water-methanol containing formic acid is taken as the mobile phase for gradient elution; and the eluent is subjected to mass spectrometric detection. The detection method is characterized in that the organic solvent extraction method is adopted for carrying out the sample pretreatment according to the practical situation of the sample and the different detection sensitivity requirements; norfloxacin-D5 is taken as the internal standard; the C18 chromatographic columns are adopted for separation; and the water-methanol containing formic acid is taken as the mobile phase for gradient elution. The pretreatment process of the method is rapid and convenient, the detection result is reliable and sensitive, and the method is suitable for the analysis and the detection of the quinolone drug residues in animal food.
Description
Technical field
The present invention relates to a kind of method that detects multiple carbostyril antibiotic in the animal food simultaneously, more specifically relate to a kind of can be simultaneously to 19 kinds of HPLC-ESI-MS/MS methods that carbostyril antibiotic carries out quantitative measurement in chicken, the flesh of fish.Belong to antibiotics and divide the folding technical field.
Background technology
Quinolone is a class synthetic antibiotic class medicine, chemically relevant with nalidixic acid, its mechanism of action is the nuclear that directly acts on bacterium, the DNA gyrase that suppresses bacterium, makes enzyme not introduce otch on the dna double chain, destroy metabolism and the breeding of bacterium, rapidly kill bacteria.Initial this class medicine is used for the treatment of urinary tract infection, has developed into therapy system now and has caught, and generally used as prevention and medicine in animal feeding.In recent years, residual caused widely of these medicines in animal tissue noted.FAO (Food and Agriculture Organization of the United Nation), the joint council of the food additives expert of the World Health Organization (WHO), European Union have all formulated the maximum residue limit(MRL) of multiple QNS in animal tissue.
The various residue analysis methods of QNS mainly comprise high-efficient liquid phase technique (HPLC) and relevant therewith HPLC-UV, HPLC-FD, HPLC-DVD, LC-MS/MS, LC-ESI-MS/MS.LesleyJohnston etc. are residual with quinolones in HPLC-MS method detection fish and the marine product and fluoroquinolones, and all analytes all obtain the good recovery, and detection limit reaches 1～3mg/kg.The LC-ESI-MS-MS method of using Gery vanVyncht etc. detects 11 kinds of QNSs in the pig kidney.
But in above-mentioned LC-MS method, be research, the variety classes medicine is not still had a kind of analytical approach of versatility, so the analysis of most carbostyril antibiotics is lacked practicality at the minority carbostyril antibiotic.In addition, the drugs analysis exists tangible impurity interference in the urine sample, thereby has influenced the accuracy and the reliability of check.And the analysis operation step complexity of existing sample, analytical cycle is long, is difficult to realize the rapid screening analysis.
Summary of the invention
The objective of the invention is to overcome the defective that to measure the minority carbostyril antibiotic in the prior art, a kind of LC-MS method that can detect multiple carbostyril antibiotic effectively is provided, and this method is intended to set up measures 19 kinds of carbostyril antibiotic medicine (Enrofloxacins in the animal muscle tissue simultaneously, Ciprofloxacin, Norfloxacin, Ofloxacin, flumequine, oxolinic acid, two Flucloxacillins, sarafloxacin, Sparfloxacin, the Dan Nuosha star, fleraxacin, Marbofloxacin, the Yi Nuosha star, Orbifloxacin, Pefloxacin, acidum nalidixicum, pipemidic acid, Lomefloxacin and cinoxacin) how residual HPLC-ESI-MS/MS detection method.Tissue sample uses organic phase to extract.This method pre-treatment process is fast and convenient, and testing result is reliably sensitive, is applicable to the analyzing and testing of quinolones medicament relict in the animal food.
Technical scheme of the present invention: a kind of HPLC-ESI-MS/MS assay method that detects 19 kinds of QNSs simultaneously, comprise sample preparation, liquid phase separation, three steps of Mass Spectrometer Method, 19 kinds of carbostyril antibiotics in the tissue fluid are carried out positive ion MRM scanning, with Norfloxacin-D5 is interior mark, adopt the C18 chromatographic column to separate, with the water-methanol that contains formic acid is that moving phase is made gradient elution, and eluent is carried out Mass Spectrometer Method;
(1) preparation of standard solution
Take by weighing Enrofloxacin, Ciprofloxacin, Norfloxacin, Ofloxacin, flumequine, oxolinic acid, two Flucloxacillin, sarafloxacin, Sparfloxacin, Dan Nuosha star, fleraxacin, Marbofloxacin, Yi Nuosha star, Orbifloxacin, Pefloxacin, acidum nalidixicum, pipemidic acid, Lomefloxacin, 19 kinds of standard items 10mg of cinoxacin respectively, be dissolved in methanol constant volume respectively to 10mL, be the standard stock solution of 1mg/mL; Measure an amount of 19 kinds of standard stock solutions respectively, the hybrid standard working fluid 10 μ g/mL of 19 kinds of QNSs of preparation; The hybrid standard working fluid is mixed with the standard solution of 0.3ng/mL, 1ng/mL, 2ng/mL, 5ng/mL, 10ng/mL, 20ng/mL and 50ng/mL with methyl alcohol, HPLC-ESI-MS/MS measures, chromatographic peak area with each component is done linear regression to concentration, gets the quantitative criterion curve;
(2) sample preparation:
The blank chicken of 2.00 ± 0.02g or the fish musculature that take by weighing homogeneous place the 50mL centrifuge tube, add an amount of standard solution, and the vortex mixing after lucifuge leaves standstill 15min, adds the 10mL acetonitrile and extracts, whirling motion 15min, and the centrifugal 5min of 3500r/min filters; Residual tissue repeats to extract once with the 10mL acetonitrile, merges supernatant, dries up with nitrogen, adds 1.0mL 30% dissolve with methanol solution then and dries up thing, and 0.45 μ m membrane filtration is as tissue fluid to be measured;
(3) liquid phase separation:
Chromatographic column: C18 reverse-phase chromatographic column 150 * 2.1mm i.d.3 μ m;
Moving phase: 0.1% aqueous formic acid-methyl alcohol mixed liquor, condition of gradient elution:
Table 1HPLC-ESI-MS/MS system flow phase gradient elution requirement
Promptly the volume ratio of 0～1min, 0.1% aqueous formic acid-methyl alcohol is 90: 10,
The volume ratio of 1～4min, 0.1% aqueous formic acid-methyl alcohol is 90～10: 10～90,
The volume ratio of 4～8min, 0.1% aqueous formic acid-methyl alcohol is 10: 90,
The volume ratio of 8～8.5min, 0.1% aqueous formic acid-methyl alcohol is 10～90: 90～10,
8.5 the volume ratio of～11min 0.1% aqueous formic acid-methyl alcohol is 90: 10;
Flow velocity: 0.2mL/min;
Sample size: 25 μ L;
Column temperature: 20 ℃;
(4) Mass Spectrometer Method:
Ion gun: electric spray ion source;
Scan mode: positive ion scanning;
Detection mode: reaction of high order detects;
Electron spray capillary voltage: 4.2kV;
Capillary temperature: 350 ℃;
Assist gas flow velocity: 5L/h;
Sheath gas flow rate: 20L/h;
Multiplier voltage: 920V
Secondary collision gas: helium.
During positive ion MRM scanning analysis, the ion selector channel m/z of each carbostyril antibiotic is respectively: Enrofloxacin 360/316, Ciprofloxacin 332/231, Norfloxacin 320/276, Ofloxacin 362/318, flumequine 262/244 oxolinic acid 262/244, two Flucloxacillins 400/382, sarafloxacin 386/368, Sparfloxacin 393/292, Dan Nuosha star 358/340, fleraxacin 370/326, Marbofloxacin 363/320, Yi Nuosha star 321/303, Orbifloxacin 396/352, Pefloxacin 334/290, acidum nalidixicum 233/215, pipemidic acid 304/217, Lomefloxacin 352/308, cinoxacin 263/245, interior mark Norfloxacin-D5325/281, wherein each compound ions channel range can be ± 0.5amu.
Sample preparation adopts the organic solvent extraction method to carry out The pretreatment; Liquid phase separation adopts the direct injected method.
Density calculating method and detectability:
Calculate the concentration of these 19 kinds of carbostyril antibiotics in the tissue fluid with peak area or peak height method by internal standard method.19 kinds of carbostyril antibiotics are linear good at low strength range 0.3～50ng/mL, can satisfy the needs of quantitative test.Detectability is 0.3ng/mL.Carry out recovery experiment behind the standard solution of recovery experiment adding known quantity in the chicken or the flesh of fish, operate and the sample introduction analysis by the disposal route of sample, replicate determination 6 times, adopt the external standard method quantitative Analysis recovery according to working curve, average recovery rate is respectively: chicken 75.3%～96.3%, the flesh of fish 79.7～94.2%, in a few days and in the daytime the Variation Lines number average is less than 10%.
Beneficial effect of the present invention:
1, the inventive method sample treatment is easy and simple to handle, and matrix is noiseless to the detection by quantitative of drugs.
2, the inventive method the carbostyril antibiotic measured simultaneously comprised in the existing breed substantially in related kind, strong, highly sensitive to the detection selectivity of sample, every methodology index all can satisfy the needs of actual detected easy, reliably.
Description of drawings
The relevant criterion curve of described 19 kinds of carbostyril antibiotics, chromatography of ions figure, mass spectrogram, blank ion chromatogram are set up equal the sixth of the twelve Earthly Branches, but since length limit, only with the spectrum curve of Danofloxacin as example.
Fig. 1 Danofloxacin typical curve.
Fig. 2 Danofloxacin chromatography of ions figure.
Fig. 3 Danofloxacin mass spectrogram.
The blank pork chromatography of ions figure (not containing Danofloxacin) of Fig. 4.
Embodiment
One, experimental section
1. instrument and reagent
Accela high performance liquid chromatography (U.S. Finnigan company) comprises Autosampler and Accela pump; TSQ QuantumAccess mass spectrometer (U.S. Finnigan company); BP211D type electronic analytical balance (German Sai Duolisi sartorius); Adjustable micro sample adding appliance series (Thermo Labsystems company); KQ-250DE type ultrasonic cleaner (Kunshan Ultrasonic Instruments Co., Ltd.); Nitrogen evaporator (OrganomationAssociates, Jnc. company); WH-861. vortex mixer (Jiangsu Province Hua Lida testing equipment company); RJ-LD-IIB low speed desk centrifuge (Ruijiang Analyzer Co. Ltd., Wuxi City); 19 kinds of QNSs (Sigma aldrich company) such as Enrofloxacin, Ciprofloxacin, Norfloxacin; It is pure that other chemical reagent are analysis.
2. the preparation of standard solution
Take by weighing an amount of Enrofloxacin, Ciprofloxacin, Norfloxacin, Ofloxacin, flumequine, oxolinic acid, two Flucloxacillin, sarafloxacin, Sparfloxacin, Dan Nuosha star, fleraxacin, Marbofloxacin, Yi Nuosha star, Orbifloxacin, Pefloxacin, acidum nalidixicum, pipemidic acid, Lomefloxacin and 19 kinds of standard items 10mg of cinoxacin respectively, be dissolved in methanol constant volume respectively to 10mL, be the standard stock solution of 1mg/mL; Equivalent is measured 19 kinds of standard stock solutions respectively, the hybrid standard working fluid 10 μ g/mL of 19 kinds of QNSs of preparation; The hybrid standard working fluid is mixed with 0.3,1,2,5,10,20 and the standard solution of 50ng/mL with methyl alcohol, carries out HPLC-ESI-MS/MS and measure.Chromatographic peak area with each component is done linear regression to concentration, gets the quantitative criterion curve.
3. sample preparation
The blank chicken of 2.00 ± 0.02g or the fish musculature that take by weighing homogeneous place the 50mL centrifuge tube, add an amount of standard solution, and the vortex mixing after lucifuge leaves standstill 15min, adds the 10mL acetonitrile and extracts, whirling motion 15min, and the centrifugal 5min of 3500r/min filters; Residual tissue repeats to extract once with the 10mL acetonitrile, merges supernatant, dries up with nitrogen, adds 1.0mL 30% dissolve with methanol solution then and dries up thing, and 0.45 μ m membrane filtration is as tissue fluid to be measured.
4. chromatographic condition
Chromatographic column: C18 reverse-phase chromatographic column (150 * 2.1mm i.d.3 μ m)
Flow velocity: 0.2mL/min
Sample size: 25 μ L
Column temperature: 20 ℃
Moving phase: 0.1% aqueous formic acid-methyl alcohol, condition of gradient elution: 0～1min, 0.1% formic acid and 10% methyl alcohol; 1～4min, 0.1% formic acid and 10%～90% methyl alcohol; 4～8min, 0.1% formic acid and 90% methyl alcohol; 8～8.5min, 0.1% formic acid and 90%～10% methyl alcohol; 8.5～11min, 0.1% formic acid and 10% methyl alcohol
5. mass spectrum condition
Ion gun: electric spray ion source
Scan mode: positive ion scanning
Detection mode: reaction of high order detects
Electron spray capillary voltage: 4.2kV
Capillary temperature: 350 ℃
Assist gas flow velocity: 5L/h
Sheath gas flow rate: 20L/h
Multiplier voltage: 920 volts
Secondary collision gas: helium
Other conditions see Table 2.
Table 2HPLC-ESI-MS/MS method is measured the setting of electric spray ion source
Annotate: the quota ion that is that is added with underscore.
6. the drafting of typical curve
Getting blank animal tissue extracts by described method, in sample, add 0,0.50,1.00,2.00,5.00,10.00,20.00 respectively, the hybrid standard working fluid of the QNS (QNs) of 50.00ng/mL concentration, dry up, with 30% methanol solution constant volume 1mL, through the membrane filtration of 0.45 μ m, HPLC-ESI-MS/MS measures.Each concentration establish 3 parallel, and sample introduction three times is a horizontal ordinate with the concentration of standard operation liquid, the peak area of the quantitative daughter ion of each medicine is an ordinate, the drawing standard curve.
7. the mensuration of detectability
Detectability is meant the minimum sample size that be able to produce in the time of can recognizing the sample peak on noise background.Be commonly defined as the sample concentration that to recognize when the sample peak-to-peak signal is twice in noise signal.
8. the mensuration of accuracy, precision, repeatability
Accuracy represents that with the recovery that tissue adds sample precision is used with the coefficient of variation of the recovery of batch sample and represented.Repeatability with picked at random 3 days on average in the daytime the coefficient of variation represent.
Get the 2.00g chicken or the flesh of fish, with 0.3ng/g, 1.0ng/g, three interpolation levels of 10ng/g, handle by above-mentioned sample-pretreating method, HPLC-ESI-MS/MS detects.According to the peak area of each component, calculate the recovery and the coefficient of variation of respective concentration.Accuracy and replica test picked at random were measured on the 3rd, measure a collection of every day, each adds concentration and gets 6 samples at random, the average recovery rate of being measured in 3rd is the accuracy of this method, 3 days day within variance coefficient is the precision of this method, and 3 days the coefficient of variation in the daytime is the repeatability of this method.
Two, experimental result
1. separating resulting
This law analysis speed is fast, and finishing once to analyze only needs 11min.Under this experiment condition, blank sample is all noiseless to 19 kinds of medicines and interior target analysis.The chromatogram that blank tissue fluid sample adds medicine is seen Fig. 1.
2. testing result
1) typical curve, the range of linearity and detection limit
Adopt the blank sample extract to prepare employed a series of matrix standard operation solution, the drawing standard curve carries out quantitatively, eliminates the ion inhibition that brings because of the matrix influence to quantitative measurement.Under the top condition of determining, measure.To concentration (X) drawing standard curve, linear relationship and related coefficient see Table 3 with the peak area (Y) of each component.The result shows that 19 kinds of QNs are linear good at low strength range 0.3～50ng/mL, can satisfy the needs of quantitative test.
Table 3 linear analysis, related coefficient and detection limit
2) recovery and precision
The recovery is carried out recovery experiment after testing the standard solution that adds people's known quantity in the chicken or the flesh of fish, operate and the sample introduction analysis by the disposal route of sample, replicate determination 6 times, adopt the external standard method quantitative Analysis recovery according to working curve, average recovery rate is respectively chicken 75.3%～96.3%, the flesh of fish 79.7～94.2%, and in a few days and in the daytime the Variation Lines number average is less than 10%.
The recovery and the coefficient of variation (n=6) in table 4 flesh of fish
The recovery in table 5 chicken and the coefficient of variation (n=6)
Claims (3)
1, a kind of HPLC-ESI-MS/MS assay method that detects 19 kinds of QNSs simultaneously, comprise sample preparation, liquid phase separation, three steps of Mass Spectrometer Method, it is characterized in that 19 kinds of carbostyril antibiotics in the tissue fluid are carried out positive ion MRM scanning, with Norfloxacin-D5 is interior mark, adopt the C18 chromatographic column to separate, with the water-methanol that contains formic acid is that moving phase is made gradient elution, and eluent is carried out Mass Spectrometer Method;
(1) preparation of standard solution
Take by weighing Enrofloxacin, Ciprofloxacin, Norfloxacin, Ofloxacin, flumequine, oxolinic acid, two Flucloxacillin, sarafloxacin, Sparfloxacin, Dan Nuosha star, fleraxacin, Marbofloxacin, Yi Nuosha star, Orbifloxacin, Pefloxacin, acidum nalidixicum, pipemidic acid, Lomefloxacin, 19 kinds of standard items 10mg of cinoxacin respectively, be dissolved in methanol constant volume respectively to 10mL, be the standard stock solution of 1mg/mL; Measure an amount of 19 kinds of standard stock solutions respectively, the hybrid standard working fluid 10 μ g/mL of 19 kinds of QNSs of preparation; The hybrid standard working fluid is mixed with the standard solution of 0.3ng/mL, 1ng/mL, 2ng/mL, 5ng/mL, 10ng/mL, 20ng/mL and 50ng/mL with methyl alcohol, HPLC-ESI-MS/MS measures, chromatographic peak area with each component is done linear regression to concentration, gets the quantitative criterion curve;
(2) sample preparation:
The blank chicken of 2.00 ± 0.02g or the fish musculature that take by weighing homogeneous place the 50mL centrifuge tube, add an amount of standard solution, and the vortex mixing after lucifuge leaves standstill 15min, adds the 10mL acetonitrile and extracts, whirling motion 15min, and the centrifugal 5min of 3500r/min filters; Residual tissue repeats to extract once with the 10mL acetonitrile, merges supernatant, dries up with nitrogen, adds 1.0mL 30% dissolve with methanol solution then and dries up thing, and 0.45 μ m membrane filtration is as tissue fluid to be measured;
(3) liquid phase separation:
Chromatographic column: C18 reverse-phase chromatographic column 150 * 2.1mm i.d.3 μ m;
Moving phase: 0.1% aqueous formic acid-methyl alcohol mixed liquor, condition of gradient elution:
The volume ratio of 0～1min, 0.1% aqueous formic acid-methyl alcohol is 90: 10,
The volume ratio of 1～4min, 0.1% aqueous formic acid-methyl alcohol is 90～10: 10～90,
The volume ratio of 4～8min, 0.1% aqueous formic acid-methyl alcohol is 10: 90,
The volume ratio of 8～8.5min, 0.1% aqueous formic acid-methyl alcohol is 10～90: 90～10,
8.5 the volume ratio of～11min 0.1% aqueous formic acid-methyl alcohol is 90: 10;
Flow velocity: 0.2mL/min;
Sample size: 25 μ L;
Column temperature: 20 ℃;
(4) Mass Spectrometer Method:
Ion gun: electric spray ion source;
Scan mode: positive ion scanning;
Detection mode: reaction of high order detects;
Electron spray capillary voltage: 4.2kV;
Capillary temperature: 350 ℃;
Assist gas flow velocity: 5L/h;
Sheath gas flow rate: 20L/h;
Multiplier voltage: 920V
Secondary collision gas: helium.
2, the HPLC-ESI-MS/M assay method of QNS according to claim 1, when it is characterized in that positive ion MRM scanning analysis, the ion selector channel m/z of each carbostyril antibiotic is respectively: Enrofloxacin 360/316, Ciprofloxacin 332/231, Norfloxacin 320/276, Ofloxacin 362/318, flumequine 262/244 ， oxolinic acid 262/244, two Flucloxacillins 400/382, sarafloxacin 386/368, Sparfloxacin 393/292, Dan Nuosha star 358/340, fleraxacin 370/326, Marbofloxacin 363/320, Yi Nuosha star 321/303, Orbifloxacin 396/352, Pefloxacin 334/290, acidum nalidixicum 233/215, pipemidic acid 304/217, Lomefloxacin 352/308, cinoxacin 263/245, interior mark Norfloxacin-D5325/281, wherein each compound ions channel range can be ± 0.5amu.
3, the HPLC-ESI-MS/MS assay method of QNS according to claim 1 is characterized in that sample preparation adopts the organic solvent extraction method to carry out The pretreatment; Liquid phase separation adopts the direct injected method.
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