CN102128891B - Analysis method for simultaneously measuring residues of sulfonamide, quinolone and benzimidazole medicaments and metabolites thereof in chicken liver - Google Patents

Analysis method for simultaneously measuring residues of sulfonamide, quinolone and benzimidazole medicaments and metabolites thereof in chicken liver Download PDF

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CN102128891B
CN102128891B CN 201010595298 CN201010595298A CN102128891B CN 102128891 B CN102128891 B CN 102128891B CN 201010595298 CN201010595298 CN 201010595298 CN 201010595298 A CN201010595298 A CN 201010595298A CN 102128891 B CN102128891 B CN 102128891B
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cip
sdx
oxfen
sample
medicaments
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CN102128891A (en
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李锋格
苏敏
李晓岩
张红霞
姚伟琴
窦辉
张万权
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XINJIANG ENTRY-EXIT INSPECTION QUARANTINE BUREAU INSPECTION QUARANTINE TECHNOLOGY CENTER
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XINJIANG ENTRY-EXIT INSPECTION QUARANTINE BUREAU INSPECTION QUARANTINE TECHNOLOGY CENTER
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Abstract

The invention discloses an analysis method for simultaneously measuring residues of 12 sulfonamide medicaments, 19 quinolone medicaments and 8 benzimidazole medicaments and metabolites thereof in chicken liver by quick, easy, cheap, effective, rugged and safe (QuEChERS) extraction and purification-ultrahigh performance liquid chromatography-tandem mass spectrometry (QuEChERS-UPLC-MS/MS). The method comprises the following steps of: extracting a sample by using 1 percent acetic acid-acetonitrile solution, purifying the sample by using NH2 adsorbent, and degreasing the sample by using n-hexane; and then performing separation by using a Kromasil Eternity C18 chromatographic column (100mm*2.1mm, 2.5mum), performing gradient elution by using 0.1 percent formic acid and methanol as mobile phases, performing ionization in an electron spray positive ion (ESI<+>) mode, performing detection in a multi-reaction monitoring (MRM) mode, and performing quantification by an internal standard method. The 39 medicaments have good linearity (r is more than 0.98) in a blank adding concentration range of 5 to 100mug/kg, the average recovery rate of the medicaments in the adding level range of 10 to 50mug/kg, the relative standard deviation (RSD) is 1.5 to 23.4 percent, the limit of detection (LOD) of the 39 medicaments is 5mug/kg, and the low limit of quantification (LOQ) is 10mug/kg. The method is simple, convenient, quick, sensitive, accurate and rugged, and is suitable for confirmation and quantitative determination of the residues of the residues of the sulfonamide, quinolone and benzimidazole medicaments in the chicken liver.

Description

Measure the analytical approach of sulfamido in the chicken gizzard, quinolones, benzimidazole medicine and metabolite residue thereof simultaneously
Technical field
The present invention relates to the analytical approach that a kind of QuEChERS-UPLC-MS/MS measures sulfamido in the chicken gizzard, quinolones, benzimidazole medicine and metabolite residue thereof simultaneously.
Background technology
Sulfamido (Sulifonamides, SAs) and quinolones (quinolones, QNs) medicine is a broad-spectrum antibacterial medicine, because of it has has a broad antifungal spectrum, efficient, low toxicity, lower-price characteristic, in breeding production such as herding, aquatic products, is widely used.But excessive use might be accumulated in human body, and is harmful when accumulating concentration above certain value, and causes pathogen to produce drug resistance.Particularly sulfa drugs such as sulfamethazine possibly cause carcinogenic, teratogenesis, mutagenesis; Nalidixic Acid has been proved the interference propagating system, influences photosensitivity, carcinogenic and mutagenesis etc.Therefore, the international food code council (CAC), the U.S., European Union, Japan and China stipulate that all the MRL (MRLs) of single sulfanilamide (SN) such as sulfa drugs total amount and sulfamethazine is 100 μ g/kg in the food; According to different cultivars, tissue and drug kinds, the MRL of quinolone medicine (MRLs) is 10～6000 μ g/kg in the food.
(Benzimidazoles is one type of widely used veterinary drug in agricultural and aquaculture BMZs) to benzimidazole, is mainly used in and prevents and treats parasitic infection.Some benzimidazole can be used as adopt before with adopt the back germifuge, be used to control the fungal infection of field crops, storage fruits and vegetables.Research shows that the benzimidazole medicine shows teratogenesis and mutagenesis in animal used as test; Therefore in the medicine of restriction use and the monitored object of animal derived food residue detection are listed the benzimidazole medicine in China, the U.S., European Union, Japan and other countries or area, and have worked out MRL (MRLs).Benzimidazole medicine MRL (MRLs) in liver is 50～1000 μ g/kg.
The detection method of measuring sulfa drugs, QNS and benzimidazole medicine and metabolin thereof mainly contains liquid phase chromatography (HPLC) and liquid phase chromatography-mass spectrum/mass spectroscopy (HPLC-MS/MS).The sensitivity of HPLC is lower and structural information can't be provided; General Chang Zuowei screening technique; HPLC-MS/MS is highly sensitive, and selectivity and specificity are good, and antijamming capability is strong; Can carry out good qualitative affirmation to the sample of low concentration, be animal derived food Chinese traditional medicine method for detecting residue comparatively advanced with commonly used at present.Measure simultaneously sulfa drugs in the chicken gizzard, QNS and benzimidazole medicine and metabolite residue thereof detection method do not appear in the newspapers.
2003; The Anastassiades of agricultural research service centre of United States Department of Agriculture etc. has developed the sample-pretreating method (being called for short QuChERS) of a kind of fast (Quick), simple (Easy), cheap (Cheap), efficient (Effective), durable (Rugged), safety (Safe), is extensively adopted by a plurality of international pesticide residue analysis mechanism such as many countries and U.S. public office AC association.
Summary of the invention
Technical matters to be solved by this invention provides a kind of analytical approach of measuring sulfamido in the chicken gizzard, quinolones, benzimidazole medicine and metabolite residue thereof simultaneously.
Technical scheme of the present invention is following:
A kind of analytical approach of measuring sulfamido in the chicken gizzard, quinolones, benzimidazole medicine and metabolite residue thereof simultaneously, testing sample extracts with 1% acetate-acetonitrile solution, NH 2Adsorbent purifies, the normal hexane degreasing; Separate with Kromasil Eternity C-18 chromatographic column then, carry out gradient elution with 0.1% formic acid and methyl alcohol as moving phase, the ionization of electron spray positive ion mode, multiple-reaction monitoring mode detection, inner mark method ration.
Described analytical approach, the chromatographic condition of said chromatographic column is: Kromasil Eternity C-18 chromatographic column is 100mm * 2.1mm, 2.5 μ m; Column temperature: 35 ℃; Sample chamber temperature: 7 ℃; Sample size: 5 μ L; Flow velocity is 0.25mL/min; Mobile phase A: 0.1% formic acid; Mobile phase B: methyl alcohol; Sulfa drugs and benzimidazole medicine gradient elution program are seen table 1, and quinolone medicine gradient elution program is seen table 2.
Table 1 sulfa drugs and benzimidazole medicine gradient elution program
Time/min Mobile phase A (0.1% formic acid)/% Mobile phase B (methyl alcohol)/%
0.00 90 10
3.50 75 25
5.50 45 55
7.00 10 90
8.00 10 90
8.10 90 10
10.50 90 10
Table 2 quinolone medicine gradient elution program
Time/min Mobile phase A (0.1% formic acid)/% Mobile phase B (methyl alcohol)/%
0.00 90 10
3.50 85 15
4.00 65 35
7.00 45 55
7.50 0 100
8.50 0 100
8.70 90 10
12.00 90 10
Described analytical approach, said mass spectrum condition is: electric spray ion source (ESI +); Capillary voltage is 3.2kV; Extraction voltage is 4.0V; Sextupole bar voltage is 0.1V in advance; The source temperature is 120 ℃; The desolventizing temperature is 380 ℃: desolventizing gas speed is 800L/h; Taper hole blowback air speed is 60L/h; Adopt multiple-reaction monitoring (MRM) pattern, other mass spectrophotometry parameters are seen table 3.
43 kinds of medicine tandem mass spectrums of table 3 parameter, 39 kinds of medicine linear equations, related coefficient, internal standard compound
Medicine Parent ion Daughter ion Taper hole voltage Collision voltage Linear equation Related coefficient Internal standard compound
SDZ 251.1 107.9 *，155.8 25 23，15 0.0545394x-0.0358695 0.990326 SDX-D3
SMT 281.2 155.9 *，215.0 30 18，18 0.0776182x-0.0329272 0.993806 SDX-D3
SDMD 279.2 155.9 *，186.0 30 20，16 0.124003x-0.0615372 0.993284 SDX-D3
SQX 301.1 107.9 *，155.9 30 28，16 0.231041x-0.112713 0.994049 SDX-D3
SDM 311.1 155.9 *，218.0 35 20，19 0.2132045x-0.103218 0.990521 SDX-D3
SMM 281.1 155.8 *，215.0 30 18，19 0.0945117x-0.0179006 0.996461 SDX-D3
SMPD 281.2 125.9 *，155.9 30 19，17 0.174534x-0.15152 0.991663 SDX-D3
SMX 254.2 107.9 *，155.9 28 20，15 0.0626221x-0.0176093 0.995120 SDX-D3
ST 256.1 107.9 *，155.9 25 23，16 0.0895381x-0.0744449 0.9901234 SDX-D3
SPD 250.1 155.9 *，184.1 28 15，17 0.0802019x-0.0994343 0.989650 SDX-D3
SMR 265.2 155.9 *，171.9 28 17，17 0.07421281x-0.0582144 0.988185 SDX-D3
SCP 285.1 107.9 *，155.9 28 22，16 0.0468546x-0.032339 0.997840 SDX-D3
ENR 360.2 245.1 *，316.2 27 27，18 0.741609x-0.30227 0.990882 CIP-D8
CIP 332.1 288.2 *，314.3 30 15，20 0.395879x+0.0855739 0.989268 CIP-D8
NOR 320.2 276.2 *，302.2 30 17，15 0.472468x-0.638422 0.986282 CIP-D8
OFL 362.2 261.1 *，318.2 30 24，18 0.869864x-0.668885 0.987215 CIP-D8
DIF 400.2 299.1 *，356.1 25 29，18 0.348825x-0.60357 0.991236 CIP-D8
OXO 262.2 159.8 *，244.0 28 35，15 0.1，31377x-0.829934 0.987547 CIP-D8
FLU 262.2 202.0 *，244.1 25 33，18 2.52021x-2.63326 0.987300 CIP-D8
SAR 386.3 342.1 *，368.0 33 19，23 0.426364x-0.217379 0.995877 CIP-D8
SPA 393.3 292.2 *，349.2 31 20，24 0.984334x-0.958516 0.985680 CIP-D8
DAN 358.3 81.9 *，340.3 33 43，22 1.06837x-0.683126 0.995722 CIP-D8
FLE 370.3 269.2 *，326.2 30 25，18 0.357517x-0.400779 0.986672 CIP-D8
MAR 363.3 71.9 *，320.2 28 20，15 0.809107x-0.398303 0.996266 CIP-D8
ENO 321.3 232.2 *，303.1 30 35，15 0.806264x-0.629923 0.992429 CIP-D8
ORB 396.3 295.2 *，352.2 32 20，15 0.406847x-0.171918 0.997260 CIP-D8
PIP 304.3 189.0 *，217.1 28 33，18 0.309149x-0.236534 0.987886 CIP-D8
PEF 334.4 233.1 *，290.3 30 25，18 0.995708x-1.0252 0.986952 CIP-D8
LOM 352.4 265.2 *，308.2 28 22，17 0.5143369x-0.414243 0.993991 CIP-D8
CIN 263.2 217.2 *，245.1 22 20，15 0.586644x-0.559125 0.988201 CIP-D8
NAL 233.3 187.1 *，215.2 22 23，13 2.92559x-2.65157 0.986454 CIP-D8
OXFEN 316.2 158.9 *，191.1 35 32，22 0.543634x-0.383894 0.993634 OXFEN-D3
FEN 300.2 159.0 *，268.2 32 35，21 1.13875x-0.949201 0.986857 0XFEN-D3
ALB 266.2 191.0 *，234.2 35 30，20 0.907718x-0.872795 0.995807 OXFEN-D3
MEB 296.2 105.0 *，264.2 37 32，20 0.735447x+0.211597 0.992393 OXFEN-D3
ASOX 282.2 208.1 *，240.1 30 25，15 0.141177x-0.114048 0.994715 OXFEN-D3
ASF 298.1 158.8 *，266.0 33 36，20 0.59365x-0.643332 0.992976 OXFEN-D3
AASF 240.1 132.8 *，198.0 35 28，19 0.235948x-0.37909 0.994631 AASF-D3
OXFSUL 332.2 158.9 *，300.1 40 36，20 0.426846x-0.206383 0.997059 OXFEN-D3
SDX-D3 314.2 155.9 35 17 -- -- --
CIP-D8 340.1 296.1 * 30 18 -- -- --
OXFEN-D3 319.0 193.9 33 22 -- -- --
AASF-D3 243.0 132.8 37 28 -- -- --
The present invention combines QuEChERS method and Ultra Performance Liquid Chromatography method-mass spectrum/mass spectroscopy (UPLC-MS/MS), set up the QuEChERS-UPLC-MS/MS method measure simultaneously sulfa drugs in the chicken gizzard, QNS and benzimidazole medicine and metabolite residue thereof detection method.Extract sulfa drugs, QNS and benzimidazole medicine and metabolite residue thereof in the chicken gizzard, NH with 1% acetate-acetonitrile solution 2Adsorbent purifies, the normal hexane degreasing, and UPLC-MS/MS measures.
This method has shortened the time of pre-treatment; Organic reagent consumption few (15mL); Discarded object is few, environmental protection; Reduce matrix interference, improved purification efficiency.The result shows that this method is easy, quick, accurate, durable, low-cost, is fit to sulfa drugs, QNS and benzimidazole medicine and metabolite residue conclusive evidence and quantitative measurement in the chicken gizzard.
Description of drawings
Fig. 1 adds 10 μ g/kg sulphadiazine (SDZ) chicken gizzard sample MRM figure;
Fig. 2 adds 10 μ g/kg sulphathiazole (ST) chicken gizzard sample MRM figure;
Fig. 3 adds 50 μ g/kg rosickyite and reaches amino sulfone-D3 (AASF-D3) chicken gizzard of azoles sample MRM figure;
Fig. 4 adds 10 μ g/kg rosickyite and reaches amino sulfone (AASF) chicken gizzard of azoles sample MRM figure;
Fig. 5 adds 10 μ g/kg sulfapryidine (SPD) chicken gizzard sample MRM figure;
Fig. 6 adds 10 μ g/kg sulfamethyldiazine (SMR) chicken gizzard sample MRM figure;
Fig. 7 adds 10 μ g/kg sulfanilamide (SN)-5 Sulfamonomethoxine (SMT) chicken gizzard sample MRM figure;
Fig. 8 adds 10 μ g/kg sulfadimidine (SDMD) chicken gizzard sample MRM figure;
Fig. 9 adds 10 μ g/kg kynix (SMPD) chicken gizzard sample MRM figure;
Figure 10 adds 10 μ g/kg pipemidic acid (PIP) chicken gizzard sample MRM figure;
Figure 11 adds 10 μ g/kg Marbofloxacin (MAR) chicken gizzard sample MRM figure;
Figure 12 adds 10 μ g/kg fleraxacin (FIE) chicken gizzard sample MRM figure;
Figure 13 adds 10 μ g/kg Ofloxacin (OFL) chicken gizzard sample MRM figure;
Figure 14 adds 10 μ g/kg Yi Nuosha star (ENO) chicken gizzard sample MRM figure;
Figure 15 adds 10 μ g/kg Pefloxacin (PEF) chicken gizzard sample MRM figure;
Figure 16 adds 10 μ g/kg cistosulfa (SCP) chicken gizzard sample MRM figure;
Figure 17 adds 10 μ g/kg Norfloxacin (NOR) chicken gizzard sample MRM figure;
Figure 18 adds 50 μ g/kg Ciprofloxacin-D8 (CIP-D8) chicken gizzard sample MRM figure;
Figure 19 adds 10 μ g/kg Enrofloxacin (ENR) chicken gizzard sample MRM figure;
Figure 20 adds 10 μ g/kg Ciprofloxacin (CIP) chicken gizzard sample MRM figure;
Figure 21 adds 10 μ g/kg sulfamethoxazole (SMX) chicken gizzard sample MRM figure;
Figure 22 adds 10 μ g/kg Dan Nuosha star (DAN) chicken gizzard sample MRM figure;
Figure 23 adds 10 μ g/kg Lomefloxacin (LOM) chicken gizzard sample MRM figure;
Figure 24 adds 10 μ g/kg Orbifloxacin (ORB) chicken gizzard sample MRM figure;
Figure 25 adds 10 μ g/kg daimeton (SMM) chicken gizzard sample MRM figure;
Figure 26 adds two Flucloxacillin (DIF) the chicken gizzard sample MRM figure of 10 μ g/kg;
Figure 27 adds 50 μ g/kg fanasil-D3 (SDX-D3) chicken gizzard sample MRM figure;
Figure 28 adds 10 μ g/kg sarafloxacin (SAR) chicken gizzard sample MRM figure;
Figure 29 adds 10 μ g/kg Sparfloxacin (SPA) chicken gizzard sample MRM figure;
Figure 30 adds 10 μ g/kg rosickyite and reaches azoles sulfoxide (ASOX) chicken gizzard sample MRM figure;
Figure 31 adds 10 μ g/kg madribon (SDM) chicken gizzard sample MRM figure;
Figure 32 adds 10 μ g/kg rosickyite and reaches azoles sulfone (ASF) chicken gizzard sample MRM figure;
Figure 33 adds 10 μ g/kg sulfaquinoxaline (SQX) chicken gizzard sample MRM figure;
Figure 34 adds 10 μ g/kg cinoxacin (CIN) chicken gizzard sample MRM figure;
Figure 35 adds 50 μ g/kg benzene Omeprazole-D3 (OXFEN-D3) chicken gizzard sample MRM figure;
Figure 36 adds 10 μ g/kg benzene Omeprazole (OXFEN) chicken gizzard sample MRM figure;
Figure 37 adds 10 μ g/kg benzene Omeprazole sulfone (OXFSUL) chicken gizzard sample MRM figure;
Figure 38 adds 10 μ g/kg oxolinic acid (OXO) chicken gizzard sample MRM figure;
Figure 39 adds 10 μ g/kg rosickyite and reaches azoles (ALB) chicken gizzard sample MRM figure;
Figure 40 adds 10 μ g/kg mebendazol (MEB) chicken gizzard sample MRM figure;
Figure 41 adds 10 μ g/kg benzene sulphur and reaches azoles (FEN) chicken gizzard sample MRM figure;
Figure 42 adds 10 μ g/kg Nalidixic Acid (NAL) chicken gizzard sample MRM figure;
Figure 43 adds 10 μ g/kg flumequine (FLU) chicken gizzard sample MRM figure.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment, the present invention is elaborated.
1 experimental section
1.1 instrument and reagent
ACQUITY UPLC-Quattro premier XE TMGC-MS (U.S. Waters company); High speed freezing centrifuge (Italian Kontron company); Wrist formula oscillator (U.S. Burrell company); Nitrogen evaporator (U.S. Organomation company); The cutter formula is ground homogeneous appearance (German Retsch company); MS3 turbine mixer (IKA company); Compact centrifuge; 1.5mL the full recovery sample bottle of screw thread mouth (U.S. Waters company).
Amino (NH 2) adsorbent (40～63 μ m), Beijing Xiang company of shaking; Filter membrane: regenerated cellulose, 0.2 μ m, 13mm (U.S. Agilent company); Methyl alcohol, acetonitrile, formic acid, normal hexane (chromatographically pure); Dimethyl sulfoxide (DMSO) (top grade is pure); Glacial acetic acid, anhydrous sodium sulfate (analyzing pure); Water is ultrapure water.
Standard items: sulphadiazine (Sulfadiazine, SDZ), sulfanilamide (SN)-5 Sulfamonomethoxine (Sulfameter, SMT), sulfadimidine (Sulfadimidine; SDMD), sulfaquinoxaline (Sulfaquinoxaline, SQX), madribon (Sulfadimethoxine, SDM), daimeton (Sulfamonomethoxine; SMM), kynix (Sulfamethoxypyridazine, SMPD), sulfamethoxazole (Sulfamethoxazole, SMX), sulphathiazole (Sulfathiazol; ST), sulfapryidine (Sulfapyridine, SPD), sulfamethyldiazine (Sulfamerazine, SMR), cistosulfa (Sulfachloropyridazine; SCP), Enrofloxacin (enrofloxacin, ENR), Ciprofloxacin (ciprofloxacin hydrochloride), Norfloxacin (norfloxacin, NOR), Ofloxacin (ofloxacin; OFL), two Flucloxacillin (difloxacin, DIF), oxolinic acid (oxolinic acid, OXO), flumequine (flumequine; FLU), sarafloxacin (sarafloxacin, SAR), Sparfloxacin (sparfloxacin, SPA), Dan Nuosha star (danofloxacin; DAN), fleraxacin (fleroxacin, FLE), Marbofloxacin (marbofloxacin, MAR), Yi Nuosha star (enoxacin; ENO), Orbifloxacin (orbifloxacin, ORB), pipemidic acid (pipmidic acid, PIP), Pefloxacin (pefloxacin; PEF), Lomefloxacin (lomefloxacin, LOM), cinoxacin (cinoxacin, CIN), Nalidixic Acid (nalidixic acid; NAL), Ciprofloxacin-D8 (ciprofloxacin-D8, CIP-D8), the benzene Omeprazole (Oxfendazole, OXFEN), benzene sulphur reaches azoles (Fenbendazole; FEN), rosickyite reaches azoles (Albendazole; ALB), rosickyite reach the azoles sulfoxide (Albendazole sulfoxide, ASOX), rosickyite reach the azoles sulfone (Albendazole sulfone, ASF), rosickyite reaches the amino sulfone (Albendazole-2-aminosulfone of azoles; AASF), (Mebendazole is MEB) all available from German Dr.Ehrenstorfer company for mebendazol.Benzene Omeprazole sulfone (Oxfendazole sulfone; OXFSUL), fanasil-D3 (Sulfadoxine-D3; SDX-D3), benzene Omeprazole-D3 (Oxfendazole-D3; OXFEN-D3), rosickyite reaches the amino sulfone-D3 of azoles (Albendazole-2-aminosulfone-D3, AASF-D3) all available from German WiTEGALaboratorien Berlin-Adlershof company, purity is all greater than 93.5%.It is internal standard compound that Ciprofloxacin-D8, fanasil-D3, benzene Omeprazole-D3, rosickyite reach the amino sulfone-D3 of azoles.
1.2 the preparation of standard operation liquid
Use methyl alcohol to be mixed with the standard reserving solution of mass concentration the sulfamido standard items as 1mg/mL; The benzimidazole medicine uses dimethyl sulfoxide (DMSO) to be mixed with the standard reserving solution of mass concentration as 1mg/mL; QNS is mixed with the standard reserving solution that mass concentration is 1～2mg/mL with methyl alcohol (adding a certain amount of formic acid according to variety classes); And used methyl alcohol-dimethyl sulfoxide (DMSO)-water as required (10: 50: 40; Volume ratio) solution dilution becomes sulfa drugs, benzimidazole medicine and the QNS hybrid standard working solution of suitable mass concentration, preserves the term of validity 3 months down for 4 ℃ in brown storage bottle.
1.3 chromatographic condition
Chromatographic column is Kromasil Eternity C-18 chromatographic column (100mm * 2.1mm, 2.5 μ m); Column temperature: 35 ℃; Sample chamber temperature: 7 ℃; Sample size: 5 μ L; Flow velocity is 0.25mL/min; Mobile phase A: 0.1% formic acid; Mobile phase B: methyl alcohol; Sulfa drugs and benzimidazole medicine gradient elution program are seen table 1, and quinolone medicine gradient elution program is seen table 2.
1.4 mass spectrum condition
Electric spray ion source (ESI +); Capillary voltage is 3.2kV; Extraction voltage is 4.0V; Sextupole bar voltage is 0.1V in advance; The source temperature is 120 ℃; The desolventizing temperature is 380 ℃; Desolventizing gas speed is 800L/h; Taper hole blowback air speed is 60L/h.Adopt multiple-reaction monitoring (MRM) pattern, other mass spectrophotometry parameters are seen table 3.
Table 1 sulfa drugs and benzimidazole medicine gradient elution program
Time/min Mobile phase A (0.1% formic acid)/% Mobile phase B (methyl alcohol)/%
0.00 90 10
3.50 75 25
5.50 45 55
7.00 10 90
8.00 10 90
8.10 90 10
10.50 90 10
Table 2 quinolone medicine gradient elution program
Time/min Mobile phase A (0.1% formic acid)/% Mobile phase B (methyl alcohol)/%
0.00 90 10
3.50 85 15
4.00 65 35
7.00 45 55
7.50 0 100
8.50 0 100
8.70 90 10
12.00 90 10
43 kinds of medicine tandem mass spectrums of table 3 parameter, 39 kinds of medicine linear equations, related coefficient, internal standard compound
Medicine Parent ion Daughter ion Taper hole voltage Collision voltage Linear equation Related coefficient Internal standard compound
SDZ 251.1 107.9 *，155.8 25 23，15 0.0545394x-0.0358695 0.990326 SDX-D3
SMT 281.2 155.9 *，215.0 30 18，18 0.0776182x-0.0329272 0.993806 SDX-D3
SDMD 279.2 155.9 *，186.0 30 20，16 0.124003x-0.0615372 0.993284 SDX-D3
SQX 301.1 107.9 *，155.9 30 28，16 0.231041x-0.112713 0.994049 SDX-D3
SDM 311.1 155.9 *，218.0 35 20，19 0.2132045x-0.103218 0.990521 SDX-D3
SMM 281.1 155.8 *，215.0 30 18，19 0.0945117x-0.0179006 0.996461 SDX-D3
SMPD 281.2 125.9 *，155.9 30 19，17 0.174534x-0.15152 0.991663 SDX-D3
SMX 254.2 107.9 *，155.9 28 20，15 0.0626221x-0.0176093 0.995120 SDX-D3
ST 256.1 107.9 *，155.9 25 23，16 0.0895381x-0.0744449 0.9901234 SDX-D3
SPD 250.1 155.9 *，184.1 28 15，17 0.0802019x-0.0994343 0.989650 SDX-D3
SMR 265.2 155.9 *，171.9 28 17，17 0.07421281x-0.0582144 0.988185 SDX-D3
SCP 285.1 107.9 *，155.9 28 22，16 0.0468546x-0.032339 0.997840 SDX-D3
ENR 360.2 245.1 *?316.2 27 27，18 0.741609x-0.30227 0.990882 CIP-D8
CIP 332.1 288.2 *，314.3 30 15，20 0.395879x+0.0855739 0.989268 CIP-D8
NOR 320.2 276.2 *，302.2 30 17，15 0.472468x-0.638422 0.986282 CIP-D8
OFL 362.2 261.1 *，318.2 30 24，18 0.869864x-0.668885 0.987215 CIP-D8
DIF 400.2 299.1 *，356.1 25 29，18 0.348825x-0.60357 0.991236 CIP-D8
OXO 262.2 159.8 *，244.0 28 35，15 0.1，31377x-0.829934 0.987547 CIP-D8
FLU 262.2 202.0 *，244.1 25 33，18 2.52021x-2.63326 0.987300 CIP-D8
SAR 383.3 342.1 *，368.0 33 19，23 0.426364x-0.217379 0.995877 CIP-D8
SPA 393.3 292.2 *，349.2 31 20，24 0.984334x-0.958516 0.985680 CIP-D8
DAN 358.3 81.9 *，340.3 33 43，22 1.06837x-0.683126 0.995722 CIP-D8
FLE 370.3 269.2 *，326.2 30 25，18 0.357517x-0.400779 0.986672 CIP-D8
MAR 363.3 71.9 *，320.2 28 20，15 0.809107x-0.398303 0.996266 CIP-D8
ENO 321.3 232.2 *，303.1 30 35，15 0.806264x-0.629923 0.992429 CIP-D8
ORB 396.3 295.2 *，352.2 32 20，15 0.406847x-0.171918 0.997260 CIP-D8
PIP 304.3 189.0 *，217.1 28 33，18 0.309149x-0.236534 0.987886 CIP-D8
PEF 334.4 233.1 *，290.3 30 25，18 0.995708x-1.0252 0.986952 CIP-D8
LOM 352.4 265.2 *，308.2 28 22，17 0.5143369x-0.414243 0.993991 CIP-D8
CIN 263.2 217.2 *，245.1 22 20，15 0.586644x-0.559125 0.988201 CIP-D8
NAL 233.3 187.1 *，215.2 22 23，13 2.92559x-2.65157 0.986454 CIP-D8
OXFEN 316.2 158.9 *，191.1 35 32，22 0.543634x-0.383894 0.993634 OXFEN-D3
FEN 300.2 159.0 *，268.2 32 35，21 1.13875x-0.949201 0.986857 OXFEN-D3
ALB 266.2 191.0 *，234.2 35 30，20 0.907718x-0.872795 0.995807 OXFEN-D3
MEB 296.2 105.0 *，264.2 37 32，20 0.735447x+0.211597 0.992393 OXFEN-D3
ASOX 282.2 208.1 *，240.1 30 25，15 0.141177x-0.114048 0.994715 OXFEN-D3
ASF 298.1 158.8 *，266.0 33 36，20 0.59365x-0.643332 0.992976 OXFEN-D3
AASF 240.1 132.8 *，198.0 35 28，19 0.235948x-0.37909 0.994631 AASF-D3
OXFSUL 332.2 158.9 *，300.1 40 36，20 0.426846x-0.206383 0.997059 OXFEN-D3
SDX-D3 314.2 155.9 35 17 -- -- --
CIP-D8 340.1 296.1 * 30 18 -- -- --
OXFEN-D3 319.0 193.9 33 22 -- -- --
AASF-D3 243.0 132.8 37 28 -- -- --
*Quota ion (Quantitative ions)
1.5 sample preparation
Chicken gizzard is cut into small pieces, grinds homogeneous appearance 2500r/min with the cutter formula and be crushed to pulpous state.Take by weighing the 5.00g chicken gizzard in the 50mL centrifuge tube, add four kinds of internal standard compounds of 0.25 μ g, add 15mL1% acetate-acetonitrile solution, shaken, wrist formula oscillator vibration 20min adds the 6g anhydrous sodium sulfate, vortex 1min, the centrifugal 10min of 6000r/min.
Pipette the 4.5mL supernatant to the 15mL centrifuge tube, add the amino (NH of 200mg 2), vortex 2min, the centrifugal 10min of 4500r/min.Accurately pipette in 3mL supernatant to the 5mL scale test tube, under 45 ℃, under nitrogen, slowly dry up; Add 1mL methyl alcohol-dimethyl sulfoxide (DMSO)-water (10: 50: 40, volume ratio) solution dissolved residue, vortex 1min; Add the 2mL normal hexane, vortex 1min, the centrifugal 5min of 4500r/min; Discard the normal hexane layer, repeat 2 times.To sample bottle, supply LC-MS/MS to measure with 0.2 μ m regenerated cellulose membrane filtration.
2 results and discussion
2.1 the selection of sample pre-treatments condition and optimization
The chicken gizzard complicated component contains amounts of protein, fat, carbohydrates, vitamin nutritional labelings such as (being mainly lactochrome).According to method for distilling of the present invention, acetonitrile can make protein denaturation form deposition, removes through after centrifugal, and anhydrous sodium sulfate is removed the moisture in the matrix, amino (NH 2) adsorbent removes in the extract carbohydrates and part fat, the extract color be a golden yellow, and this extract is slowly dried up under nitrogen; Add 1mL methyl alcohol-dimethyl sulfoxide (DMSO)-water (10: 50: 40, volume ratio) solution dissolved residue, find to have a little yellow mercury oxide; Add 2mL normal hexane solubilized sediment, after centrifugal, remove, repeat 2 times; It is limpid to filter back solution, and recovery test meets the requirements.
Experiment is also selected constant volume solution, find that solution is clarified when using methanol-water (90: 10, volume ratio) when being constant volume solution, but chromatographic peak profile changes behind the sample introduction, and sensitivity descends, and retention time is unstable; When using methanol-water (20: 80, volume ratio), can not dissolve fully, be turbid solution, high speed centrifugation and membrane filtration all can not solve.(Dimethyl sulfoxide is a kind of not only water-soluble but also is dissolved in the very important aprotic polar solvent of organic solvent DMSO) that very strong dissolving power is arranged to dimethyl sulfoxide (DMSO), can mix with arbitrary proportion with water.The benzimidazole medicine that needs among the present invention to measure has good dissolubility at dimethyl sulfoxide (DMSO).Through test of many times, methyl alcohol-dimethyl sulfoxide (DMSO)-water (10: 50: 40, volume ratio) solution can make residue dissolve fully; The solution clarification, chromatographic peak profile is sharp-pointed behind the sample introduction, and symmetry is good; Retention time is stable, and sensitivity does not change, and the recovery can meet the demands; It is therefore selected that methyl alcohol-dimethyl sulfoxide (DMSO)-water (10: 50: 40, volume ratio) solution is constant volume solution.
2.2 the selection of chromatographic condition and optimization
Experiment is to Kromasil Eternity C-18; BEH C18 chromatographic column compares, and the result finds: separating effect is consistent, but the sensitivity of Kromasil Eternity C-18 chromatographic column is higher; The stability of retention time is better, and the applicability of actual sample test is better, durable.The final Kromasil Eternity C-18 chromatographic column of selecting.
The adjacent Sulfamonomethoxine of sulfanilamide (SN) in the sulfa drugs, daimeton and sulfamethoxypyridazine, the flumequine in the QNS and the parent ion of oxolinic acid and daughter ion are identical, require when carrying out mass spectrophotometry and must on chromatographic column, separate.Find in the test that when the gradient elution program of use table 1 was separated three types of medicines, benzimidazole medicine and QNS retention time were very approaching, when establishment MRM, in a passage, must arrange a lot of medicines, cause sensitivity to reduce.For improving sensitivity, the gradient elution program is optimized, adopt two gradient elution programs; The gradient elution program of table 1 is separated sulfamido and benzimidazole medicine, and the gradient elution program of table 2 is separated QNS, to twice of same sample determination; Thereby realized the adjacent Sulfamonomethoxine of the sulfanilamide (SN) in the sulfa drugs, daimeton and sulfamethoxypyridazine, separating of flumequine in the QNS and oxolinic acid also makes 39 kinds of medicines obtain separating preferably simultaneously; Peak shape is sharp-pointed; Symmetry is good, and is highly sensitive, aims at determinacy and quantitatively extremely beneficial.
2.3 the elimination of sample substrate effect
The application liquid chromatography-when tandem mass spectrum was measured complex sample, matrix had enhancing or depression effect to the ionization of analyte, has a strong impact on quantitative accuracy.Find that in setting up the process of this method when proofreading and correct the mark-on sample with the solvent calibration curve, benzene sulphur reaches azoles, rosickyite and reaches azoles and the QNS recovery between 30～60%, the recovery is on the low side.The present invention adopts the blank sample that adds of series as the matrix standard solution, proofreaies and correct the mark-on sample with this calibration curve, and the recovery of 39 kinds of medicines reaches between 72～121%; Comply with relevant regulations; Therefore, the present invention adopts matrix standard solution calculate recovery rate, eliminates the matrix effect influence.
2.4 the optimization of mass spectrum condition
Under ESI (+) pattern, respectively the single standard solution of 0.5ug/L is carried out the analysis of one-level mass spectrum full scan; Obtain the molion of every kind of medicine; Be parent ion with the molion then, its daughter ion is carried out full scan, detect with the MRM pattern; On this basis taper hole voltage and impact energy are optimized, make the abundance and the ratio of the characteristic ion of selected parent ion and daughter ion composition reach best.Optimization obtains the mass spectrum condition and sees table 3.Fig. 1-Figure 43 is for adding 10 μ g/kg39 kind medicines and metabolin chicken gizzard sample MRM thereof figure.
2.4 qualitative foundation and quantivative approach
Qualitative foundation: when carrying out sample determination, if the mass chromatography peak retention time consistent with standard operation solution (variation range is within ± 2.5%) in the sample; And in the sample mass spectrogram after background correction; Selected ion all occurs; And the standard solution spectrogram that obtains under selected ion relative abundance and the approaching similarity condition of concentration is compared; The maximum scope that allows relative deviation to be no more than table 4 regulation, but then there is target compound in the judgement sample.Adopt inner mark method ration.
The maximum allowable offset of the qualitative ion relative abundance of table 4
Figure BSA00000390762500161
2.5 linear relationship, detection limit
Accurately pipette an amount of 39 kinds of sulfa drugss, benzimidazole medicine and QNS and 4 kinds of internal standard compound hybrid standard working solutions, add to respectively in the blank chicken gizzard of 5g, handle by 1.5 methods; Making content is 5,10,25; 50; The blank sample that adds of the series of 100 μ g/kg, wherein internal standard compound concentration is 50 μ g/kg, and the machine of going up is then measured.Is ordinate with the target components peak area to the ratio Y of internal standard compound peak area, and adding mass concentration X (μ g/kg) accordingly with target components is horizontal ordinate, the drawing standard curve.Each component is all linear to the ratio of internal standard compound peak area with its peak area in the scope of 5～100 μ g/kg, and the facies relationship number average is greater than 0.98.The internal standard compound of linear equation, related coefficient, use is seen table 3.
Be employed in the method for adding target components in the blank tissue; Signal to noise ratio (S/N ratio) (S/N) according to the characteristic ion chromatographic peak is detection limit (LOD) greater than 3; Signal to noise ratio (S/N ratio) (S/N) is mensuration lower bound (LOQ) greater than 10, and the LOD that obtains 39 kinds of medicines is 5 μ g/kg, and LOQ is 10 μ g/kg.
2.6 the recovery and precision
With the chicken gizzard is sample, does the interpolation test of three levels, is respectively 10 μ g/kg, 25 μ g/kg, 50 μ g/kg; Each interpolation level repeats 6 times; Carry out recovery test by 1.5, the method recovery and relative standard deviation meet the requirement of domestic and international related standards and rules, see table 5.
39 kinds of medicines of table 5 add the recovery and relative standard deviation (n=6) in blank chicken gizzard
Figure BSA00000390762500162
Figure BSA00000390762500171
Figure BSA00000390762500181
Figure BSA00000390762500191
2.7 sample determination
Use method for building up of the present invention that 27 parts of chicken gizzard samples are detected, this method is easy, fast, has good applicability and workable, and spectrogram is noiseless, does not detect 39 kinds of medicines (detect and be limited to 5 μ g/kg) at the chicken gizzard sample of being examined.
3 conclusions
Experimental result shows; The method that the QuEChERS-UPLC-MS/MS method that the present invention sets up is measured sulfa drugs in the chicken gizzard, QNS and benzimidazole medicine and metabolite residue thereof is simultaneously once extracted and can be detected 39 kinds of medicines; It is simple to have pre-treatment; Time is short, environmental protection, characteristics such as cost is low.Extract sulfa drugs, QNS and benzimidazole medicine and metabolite residue thereof in the chicken gizzard, NH with 1% acetate-acetonitrile solution 2Adsorbent purifies, the normal hexane degreasing, and UPLC-MS/MS measures.Method is easy, quick, accurate, durable, environmental protection, low cost, is fit to sulfa drugs, QNS and benzimidazole medicine and metabolite residue conclusive evidence and quantitative measurement in the chicken gizzard.
Should be understood that, concerning those of ordinary skills, can improve or conversion, and all these improvement and conversion all should belong to the protection domain of accompanying claims of the present invention according to above-mentioned explanation.

Claims (1)

1. an analytical approach of measuring sulfamido in the chicken gizzard, quinolones, benzimidazole medicine and metabolite residue thereof simultaneously is characterized in that, uses liquid chromatography-tandem mass spectrometry and measures, and testing sample extracts with 1% acetate-acetonitrile solution, NH 2Adsorbent purifies, the normal hexane degreasing; Separate with Kromasil Eternity C-18 chromatographic column then, carry out gradient elution with 0.1% formic acid and methyl alcohol as moving phase, the ionization of electron spray positive ion mode, multiple-reaction monitoring mode detection, inner mark method ration; The chromatographic condition of said chromatographic column is: Kromasil Eternity C-18 chromatographic column is 100mm * 2.1mm, 2.5 μ m; Column temperature: 35 ℃; Sample chamber temperature: 7 ℃; Sample size: 5 μ L; Flow velocity is 0.25mL/min; Mobile phase A: 0.1% formic acid; Mobile phase B: methyl alcohol; Sulfa drugs and benzimidazole medicine gradient elution program are seen table 1, and quinolone medicine gradient elution program is seen table 2;
Table 1 sulfa drugs and benzimidazole medicine gradient elution program
Time/min Mobile phase A (0.1% formic acid)/% Mobile phase B (methyl alcohol)/% 0.00 90 10 3.50 75 25 5.50 45 55 7.00 10 90 8.00 10 90 8.10 90 10 10.50 90 10
Table 2 quinolone medicine gradient elution program
Time/min Mobile phase A (0.1% formic acid)/% Mobile phase B (methyl alcohol)/% 0.00 90 10 3.50 85 15 4.00 65 35 7.00 45 55
7.50 0 100 850 0 100 8.70 90 10 12.00 90 10
The mass spectrum condition is: electric spray ion source (ESI +); Capillary voltage is 3.2kV; Extraction voltage is 4.0V; Sextupole bar voltage is 0.1V in advance; The source temperature is 120 ℃; The desolventizing temperature is 380 ℃; Desolventizing gas speed is 800L/h; Taper hole blowback air speed is 60L/h; Adopt multiple-reaction monitoring (MRM) pattern, other mass spectrophotometry parameters are seen table 3;
Table 343 kind of medicine tandem mass spectrum parameter, 39 kinds of medicine linear equations, related coefficient, internal standard compound
Medicine Parent ion Daughter ion Taper hole voltage Collision voltage Linear equation Related coefficient Internal standard compound SDZ 251.1 107.9 *，155.8 25 23，15 0.0545394x-0.0358695 0.990326 SDX-D3 SMT 281.2 155.9 *，215.0 30 18，18 0.0776182x-0.0329272 0.993806 SDX-D3 SDMD 279.2 155.9 *，186.0 30 20，16 0.124003x-0.0615372 0.993284 SDX-D3 SQX 301.1 107.9 *，155.9 30 28，16 0.231041x-0.112713 0.994049 SDX-D3 SDM 311.1 155.9 *，218.0 35 20，19 0.2132045x-0.103218 0.990521 SDX-D3 SMM 281.1 155.8 *，215.0 30 18，19 0.0945117x-0.0179006 0.996461 SDX-D3 SMPD 281.2 125.9 *，155.9 30 19，17 0.174534x-0.15152 0.991663 SDX-D3 SMX 254.2 107.9 *，155.9 28 20，15 0.0626221x-0.0176093 0.995120 SDX-D3 ST 256.1 107.9 *，155.9 25 23，16 0.0895381x-0.0744449 0.9901234 SDX-D3 SPD 250.1 155.9 *，184.1 28 15，17 0.0802019x-0.0994343 0.989650 SDX-D3 SMR 265.2 155.9 *，171.9 28 17，17 0.07421281x-0.0582144 0.988185 SDX-D3
SCP 285.1 107.9 *，155.9 28 22，16 0.0468546x-0.032339 0.997840 SDX-D3 ENR 360.2 245.1 *，316.2 27 27，18 0.741609x-0.30227 0.990882 CIP-D8 CIP 332.1 288.2 *，314.3 30 15，20 0.395879x+0.0855739 0.989268 CIP-D8 NOR 320.2 276.2 *，302.2 30 17，15 0.472468x-0.638422 0.986282 CIP-D8 OFL 362.2 261.1 *，318.2 30 24，18 0.869864x-0668885 0.987215 CIP-D8 DIF 400.2 299.1 *，356.1 25 29，18 0.348825x-0.60357 0.991236 CIP-D8 OXO 262.2 159.8 *，244.0 28 35，15 0.1.31377x-0.829934 0.987547 CIP-D8 FLU 262.2 202.0 *，244.1 25 33，18 2.52021x-2.63326 0.987300 CIP-D8 SAR 386.3 342.1 *，368.0 33 19，23 0.426364x-0.217379 0.995877 CIP-D8 SPA 393.3 292.2 *，349.2 31 20，24 0.984334x-0.958516 0.985680 CIP-D8 DAN 358.3 81.9 *，340.3 33 43，22 1.06837x-0.683126 0.995722 CIP-D8 FLE 370.3 269.2 *，326.2 30 25，18 0.357517x-0.400779 0.986672 CIP-D8 MAR 363.3 71.9 *，320.2 28 20，15 0.809107x-0.398303 0.996266 CIP-D8 ENO 321.3 232.2 *，303.1 30 35，15 0.806264x-0.629923 0.992429 CIP-D8 ORB 396.3 295.2 *，352.2 32 20，15 0.406847x-0.171918 0.997260 CIP-D8 PIP 304.3 189.0 *，217.1 28 33，18 0.309149x-0.236534 0.987886 CIP-D8 PEF 334.4 233.1 *，290.3 30 25，18 0.995708x-1.0252 0.986952 CIP-D8
LOM 352.4 265.2 *，308.2 28 22，17 0.5143369x-0.414243 0.993991 CIP-D8 CIN 263.2 217.2 *，245.1 22 20，15 0.586644x-0.559125 0.988201 CIP-D8 NAL 233.3 187.1 *，215.2 22 23，13 2.92559x-2.65157 0.986454 CIP-D8 OXFEN 316.2 158.9 *，191.1 35 32，22 0.543634x-0.383894 0.993634 OXFEN-D3 FEN 300.2 159.0 *，268.2 32 35，21 1.13875x-0.949201 0.986857 OXFEN-D3 ALB 266.2 191.0 *，234.2 35 30，20 0.907718x-0.872795 0.995807 OXFEN-D3 MEB 296.2 105.0 *，264.2 37 32，20 0.735447x+0.211597 0.992393 OXFEN-D3 ASOX 282.2 208.1 *，240.1 30 25，15 0.141177x-0.114048 0.994715 OXFEN-D3 ASF 298.1 158.8 *，266.0 33 36，20 0.59365x-0.643332 0.992976 OXFEN-D3 AASF 240.1 132.8 *，198.0 35 28，19 0.235948x-0.37909 0.994631 AASF-D3 OXFSUL 332.2 158.9 *，300.1 40 36，20 0.426846x-0.206383 0.997059 OXFEN-D3 SDX-D3 314.2 155.9 35 17 -- -- -- CIP-D8 340.1 2961 * 30 18 -- -- -- OXFEN-D3 319.0 193.9 33 22 -- -- -- AASF-D3 243.0 132.8 37 28 -- -- --
。
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