Chinese Journal of Chromatography ›› 2021, Vol. 39 ›› Issue (4): 406-414.DOI: 10.3724/SP.J.1123.2020.05012
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LIU Bolin*(), XIE Jian, ZHAO Ziwei, WANG Xiuli, SHAN Xiaomei
Received:
2020-05-29
Online:
2021-04-08
Published:
2021-03-08
Contact:
LIU Bolin
CLC Number:
LIU Bolin, XIE Jian, ZHAO Ziwei, WANG Xiuli, SHAN Xiaomei. Simultaneous determination of 11 prohibited and restricted veterinary drugs and their metabolites in animal-derived foods by ultra performance liquid chromatography-tandem mass spectrometry coupled with solid phase extraction[J]. Chinese Journal of Chromatography, 2021, 39(4): 406-414.
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URL: https://www.chrom-china.com/EN/10.3724/SP.J.1123.2020.05012
Analyte | ESI | tR/ min | Parent ion (m/z) | Product ions (m/z) | Collision energies/eV | Cone voltage/ V | IS |
---|---|---|---|---|---|---|---|
Florfenicol amine (氟苯尼考胺) | + | 0.84 | 248.1 | 230.1*/130.1 | 12/24 | 30 | florfenicol amine-D3 |
Metronidazole (甲硝唑) | + | 1.49 | 172.1 | 128.1*/82.0 | 14/22 | 30 | metronidazole-D4 |
Ronidazole (洛硝达唑) | + | 1.55 | 201 | 140.0*/55.1 | 12/20 | 24 | ronidazole-D3 |
Dimetridazole (地美硝唑) | + | 1.68 | 142.1 | 96.0*/81.0 | 16/22 | 36 | dimetridazole-D3 |
Thiamphenicol (甲砜霉素) | - | 2.2 | 354 | 185.0*/290.1 | 20/12 | 30 | thiamphenicol-D3 |
Lincomycin (林可霉素) | + | 2.43 | 407.4 | 126.1*/359.3 | 28/20 | 52 | lincomycin-D3 |
Florfenicol (氟苯尼考) | - | 2.89 | 356 | 185.0*/336.1 | 18/10 | 36 | florfenicol-D3 |
Chloramphenicol (氯霉素) | - | 3.71 | 321 | 257.0/152.0* | 10/20 | 30 | chloramphenicol-D5 |
Erythromycin A (红霉素A) | + | 4.25 | 734.5 | 158.1*/576.5 | 28/20 | 48 | erythromycin A-D6 |
Erythromycin A enol ether | + | 4.28 | 716.4 | 158.1*/83.0/558.3 | 30/42/20 | 44 | erythromycin A-D6 |
(红霉素A烯醇醚) | |||||||
Anhydro erythromycin A (脱氧红霉素A) | + | 4.42 | 716.4 | 158.1*/558.3 | 30/16 | 38 | erythromycin A-D6 |
Florfenicol amine-D3 (氟苯尼考胺-D3) | + | 0.83 | 251.2 | 233.1*/130.2 | 12/24 | 30 | |
Metronidazole-D4 (甲硝唑-D4) | + | 1.49 | 176.2 | 128.1*/82.0 | 16/26 | 30 | |
Ronidazole-D3 (洛硝达唑-D3) | + | 1.55 | 204 | 143.0*/58.0 | 20/12 | 24 | |
Dimetridazole-D3 (地美硝唑-D3) | + | 1.68 | 145 | 99.0*/83.0 | 22/16 | 36 | |
Thiamphenicol-D3 (甲砜霉素-D3) | - | 2.2 | 357.1 | 188.1*/293.1 | 20/12 | 40 | |
Lincomycin-D3 (林可霉素-D3) | + | 2.43 | 410.4 | 129.1*/362.3 | 28/20 | 52 | |
Florfenicol-D3 (氟苯尼考-D3) | - | 2.89 | 359.1 | 188.1*/339.1 | 18/10 | 36 | |
Chloramphenicol-D5(氯霉素-D5) | - | 3.71 | 326 | 157.0*/262.0 | 18/12 | 30 | |
Erythromycin A-D6 (红霉素A-D6) | + | 4.25 | 740.5 | 164.1*/582.5 | 32/20 | 48 |
Table 1 MS parameters for the 11 analytes and 9 isotope internal standards
Analyte | ESI | tR/ min | Parent ion (m/z) | Product ions (m/z) | Collision energies/eV | Cone voltage/ V | IS |
---|---|---|---|---|---|---|---|
Florfenicol amine (氟苯尼考胺) | + | 0.84 | 248.1 | 230.1*/130.1 | 12/24 | 30 | florfenicol amine-D3 |
Metronidazole (甲硝唑) | + | 1.49 | 172.1 | 128.1*/82.0 | 14/22 | 30 | metronidazole-D4 |
Ronidazole (洛硝达唑) | + | 1.55 | 201 | 140.0*/55.1 | 12/20 | 24 | ronidazole-D3 |
Dimetridazole (地美硝唑) | + | 1.68 | 142.1 | 96.0*/81.0 | 16/22 | 36 | dimetridazole-D3 |
Thiamphenicol (甲砜霉素) | - | 2.2 | 354 | 185.0*/290.1 | 20/12 | 30 | thiamphenicol-D3 |
Lincomycin (林可霉素) | + | 2.43 | 407.4 | 126.1*/359.3 | 28/20 | 52 | lincomycin-D3 |
Florfenicol (氟苯尼考) | - | 2.89 | 356 | 185.0*/336.1 | 18/10 | 36 | florfenicol-D3 |
Chloramphenicol (氯霉素) | - | 3.71 | 321 | 257.0/152.0* | 10/20 | 30 | chloramphenicol-D5 |
Erythromycin A (红霉素A) | + | 4.25 | 734.5 | 158.1*/576.5 | 28/20 | 48 | erythromycin A-D6 |
Erythromycin A enol ether | + | 4.28 | 716.4 | 158.1*/83.0/558.3 | 30/42/20 | 44 | erythromycin A-D6 |
(红霉素A烯醇醚) | |||||||
Anhydro erythromycin A (脱氧红霉素A) | + | 4.42 | 716.4 | 158.1*/558.3 | 30/16 | 38 | erythromycin A-D6 |
Florfenicol amine-D3 (氟苯尼考胺-D3) | + | 0.83 | 251.2 | 233.1*/130.2 | 12/24 | 30 | |
Metronidazole-D4 (甲硝唑-D4) | + | 1.49 | 176.2 | 128.1*/82.0 | 16/26 | 30 | |
Ronidazole-D3 (洛硝达唑-D3) | + | 1.55 | 204 | 143.0*/58.0 | 20/12 | 24 | |
Dimetridazole-D3 (地美硝唑-D3) | + | 1.68 | 145 | 99.0*/83.0 | 22/16 | 36 | |
Thiamphenicol-D3 (甲砜霉素-D3) | - | 2.2 | 357.1 | 188.1*/293.1 | 20/12 | 40 | |
Lincomycin-D3 (林可霉素-D3) | + | 2.43 | 410.4 | 129.1*/362.3 | 28/20 | 52 | |
Florfenicol-D3 (氟苯尼考-D3) | - | 2.89 | 359.1 | 188.1*/339.1 | 18/10 | 36 | |
Chloramphenicol-D5(氯霉素-D5) | - | 3.71 | 326 | 157.0*/262.0 | 18/12 | 30 | |
Erythromycin A-D6 (红霉素A-D6) | + | 4.25 | 740.5 | 164.1*/582.5 | 32/20 | 48 |
Fig. 1 Total ion current (TIC)chromatograms of the 11 prohibited and restricted veterinary drugs and their metabolites 1. florfenicol amine; 2. metronidazole; 3. ronidazole; 4. dimetridazole; 5. thiamphenicol; 6. lincomycin; 7. florfenicol; 8. chloramphenicol; 9. erythromycin A; 10. erythromycin A enol ether; 11. anhydro erythromycin A.
Fig. 2 Effect of different phosphate buffer pH values on the extraction efficiencies of the 11 prohibited and restricted veterinary drugs and their metabolites
Analyte | Linear equation | Linear range/(μg/L) | R2 | LOD/(μg/kg) | LOQ/(μg/kg) |
---|---|---|---|---|---|
Florfenicol amine | y=0.0898x-0.0035 | 0.1-50 | 0.9992 | 0.050 | 0.20 |
Metronidazole | y=0.1920x-0.0171 | 0.1-50 | 0.9972 | 0.050 | 0.20 |
Ronidazole | y=0.1535x-0.0172 | 0.1-50 | 0.9982 | 0.050 | 0.20 |
Dimetridazole | y=0.1894x-0.0155 | 0.1-50 | 0.9968 | 0.050 | 0.20 |
Thiamphenicol | y=0.0949x-0.0163 | 1.0-50 | 0.9927 | 0.50 | 1.5 |
Lincomycin | y=0.1311x-0.0088 | 0.1-50 | 0.9988 | 0.050 | 0.20 |
Florfenicol | y=0.0756x+0.0049 | 0.5-50 | 0.9971 | 0.25 | 0.80 |
Chloramphenicol | y=0.2078x+0.0066 | 0.5-50 | 0.9981 | 0.25 | 0.80 |
Erythromycin A | y=0.1283x-0.0116 | 0.2-50 | 0.9991 | 0.10 | 0.30 |
Erythromycin A enol ether | y=0.0705x-0.0099 | 0.2-50 | 0.9969 | 0.10 | 0.30 |
Anhydro erythromycin A | y=0.1414x-0.0336 | 0.2-50 | 0.9914 | 0.10 | 0.30 |
Table 2 Linear equations, linear ranges, correlation coefficients (R2), LODs, and LOQs for the 11 prohibited and restricted veterinary drugs and their metabolites
Analyte | Linear equation | Linear range/(μg/L) | R2 | LOD/(μg/kg) | LOQ/(μg/kg) |
---|---|---|---|---|---|
Florfenicol amine | y=0.0898x-0.0035 | 0.1-50 | 0.9992 | 0.050 | 0.20 |
Metronidazole | y=0.1920x-0.0171 | 0.1-50 | 0.9972 | 0.050 | 0.20 |
Ronidazole | y=0.1535x-0.0172 | 0.1-50 | 0.9982 | 0.050 | 0.20 |
Dimetridazole | y=0.1894x-0.0155 | 0.1-50 | 0.9968 | 0.050 | 0.20 |
Thiamphenicol | y=0.0949x-0.0163 | 1.0-50 | 0.9927 | 0.50 | 1.5 |
Lincomycin | y=0.1311x-0.0088 | 0.1-50 | 0.9988 | 0.050 | 0.20 |
Florfenicol | y=0.0756x+0.0049 | 0.5-50 | 0.9971 | 0.25 | 0.80 |
Chloramphenicol | y=0.2078x+0.0066 | 0.5-50 | 0.9981 | 0.25 | 0.80 |
Erythromycin A | y=0.1283x-0.0116 | 0.2-50 | 0.9991 | 0.10 | 0.30 |
Erythromycin A enol ether | y=0.0705x-0.0099 | 0.2-50 | 0.9969 | 0.10 | 0.30 |
Anhydro erythromycin A | y=0.1414x-0.0336 | 0.2-50 | 0.9914 | 0.10 | 0.30 |
Analyte | Spiked level/ (μg/kg) | Recoveries/% | RSDs/% | ||||||||
---|---|---|---|---|---|---|---|---|---|---|---|
Egg | Fish | Chicken | Milk | Egg | Fish | Chicken | Milk | ||||
Florfenicol amine | 0.2 | 97.9 | 89.7 | 98.4 | 94.0 | 11 | 13 | 10 | 14 | ||
2.0 | 93.4 | 92.9 | 94.5 | 92.5 | 1.4 | 2.2 | 6.2 | 7.2 | |||
100 | 97.1 | 100 | 94.0 | 92.3 | 6.8 | 2.4 | 11 | 4.9 | |||
Metronidazole | 0.2 | 92.5 | 84.1 | 84.1 | 86.3 | 2.0 | 3.7 | 2.7 | 3.1 | ||
2.0 | 91.0 | 83.8 | 77.9 | 81.5 | 3.3 | 1.5 | 1.1 | 3.3 | |||
20 | 98.2 | 95.9 | 107 | 103 | 5.3 | 6.3 | 2.2 | 3.3 | |||
Ronidazole | 0.2 | 92.5 | 95.4 | 98.7 | 93.7 | 4.5 | 5.0 | 2.8 | 6.8 | ||
2.0 | 96.2 | 95.3 | 95.8 | 93.6 | 2.0 | 2.9 | 2.0 | 4.8 | |||
20 | 94.4 | 93.5 | 107 | 94.8 | 1.7 | 1.9 | 4.0 | 7.3 | |||
Dimetridazole | 0.2 | 99.0 | 105 | 100 | 102 | 7.8 | 2.8 | 2.1 | 5.1 | ||
2.0 | 100 | 98.2 | 94.0 | 97.3 | 2.1 | 4.8 | 1.4 | 3.6 | |||
20 | 96.5 | 97.7 | 83.8 | 104 | 6.7 | 7.2 | 5.2 | 6.9 | |||
Thiamphenicol | 2.0 | 95.0 | 99.8 | 97.7 | 98.4 | 6.2 | 2.8 | 1.6 | 4.6 | ||
10 | 102 | 97.4 | 101 | 103 | 0.40 | 1.2 | 2.7 | 2.4 | |||
50 | 98.0 | 98.8 | 98.4 | 98.6 | 7.0 | 8.9 | 5.8 | 2.8 | |||
Lincomycin | 0.2 | 102 | 91.9 | 89.7 | 85.8 | 6.2 | 9.9 | 4.1 | 3.3 | ||
2.0 | 97.5 | 91.0 | 94.3 | 90.5 | 5.0 | 3.9 | 5.6 | 0.94 | |||
50 | 83.6 | 76.7 | 77.8 | 95.0 | 1.5 | 5.4 | 10 | 8.6 | |||
Florfenicol | 1.0 | 98.6 | 100 | 101 | 100 | 6.9 | 9.6 | 11 | 10 | ||
2.0 | 102 | 99.1 | 99.5 | 98.3 | 2.5 | 2.07 | 2.90 | 3.3 | |||
100 | 104 | 103 | 101 | 100 | 2.4 | 1.2 | 5.3 | 4.4 | |||
Chloramphenicol | 1.0 | 102 | 107 | 108 | 106 | 3.4 | 2.0 | 1.7 | 0.76 | ||
2.0 | 101 | 99.5 | 103 | 102 | 0.55 | 3.2 | 3.1 | 4.2 | |||
10 | 103 | 101 | 103 | 107 | 5.3 | 3.0 | 4.2 | 2.0 | |||
Erythromycin A | 0.3 | 87.5 | 93.5 | 90.7 | 94.7 | 4.7 | 4.2 | 1.1 | 5.5 | ||
2.0 | 86.4 | 93.9 | 92.1 | 93.7 | 0.88 | 2.1 | 4.2 | 5.2 | |||
40 | 104 | 102 | 100 | 99.7 | 5.5 | 0.8 | 4.2 | 5.6 | |||
Erythromycin A enol ether | 0.3 | 65.3 | 104 | 84.4 | 82.1 | 11 | 4.2 | 15 | 8.1 | ||
2.0 | 76.1 | 97.2 | 71.2 | 90.2 | 13 | 4.2 | 21 | 11 | |||
10 | 86.9 | 99.9 | 83.2 | 90.2 | 14 | 3.9 | 10 | 7.0 | |||
Anhydro erythromycin A | 0.3 | 101 | 86.3 | 98.7 | 94.4 | 2.7 | 5.5 | 9.3 | 6.0 | ||
2.0 | 105 | 94.6 | 96.6 | 98.8 | 0.44 | 12 | 6.2 | 7.4 | |||
10 | 105 | 95.0 | 102 | 108 | 8.8 | 16 | 4.4 | 0.85 |
Table 3 Spiked recoveries and RSDs of the 11 prohibited and restricted veterinary drugs and their metabolites in real samples (n=6)
Analyte | Spiked level/ (μg/kg) | Recoveries/% | RSDs/% | ||||||||
---|---|---|---|---|---|---|---|---|---|---|---|
Egg | Fish | Chicken | Milk | Egg | Fish | Chicken | Milk | ||||
Florfenicol amine | 0.2 | 97.9 | 89.7 | 98.4 | 94.0 | 11 | 13 | 10 | 14 | ||
2.0 | 93.4 | 92.9 | 94.5 | 92.5 | 1.4 | 2.2 | 6.2 | 7.2 | |||
100 | 97.1 | 100 | 94.0 | 92.3 | 6.8 | 2.4 | 11 | 4.9 | |||
Metronidazole | 0.2 | 92.5 | 84.1 | 84.1 | 86.3 | 2.0 | 3.7 | 2.7 | 3.1 | ||
2.0 | 91.0 | 83.8 | 77.9 | 81.5 | 3.3 | 1.5 | 1.1 | 3.3 | |||
20 | 98.2 | 95.9 | 107 | 103 | 5.3 | 6.3 | 2.2 | 3.3 | |||
Ronidazole | 0.2 | 92.5 | 95.4 | 98.7 | 93.7 | 4.5 | 5.0 | 2.8 | 6.8 | ||
2.0 | 96.2 | 95.3 | 95.8 | 93.6 | 2.0 | 2.9 | 2.0 | 4.8 | |||
20 | 94.4 | 93.5 | 107 | 94.8 | 1.7 | 1.9 | 4.0 | 7.3 | |||
Dimetridazole | 0.2 | 99.0 | 105 | 100 | 102 | 7.8 | 2.8 | 2.1 | 5.1 | ||
2.0 | 100 | 98.2 | 94.0 | 97.3 | 2.1 | 4.8 | 1.4 | 3.6 | |||
20 | 96.5 | 97.7 | 83.8 | 104 | 6.7 | 7.2 | 5.2 | 6.9 | |||
Thiamphenicol | 2.0 | 95.0 | 99.8 | 97.7 | 98.4 | 6.2 | 2.8 | 1.6 | 4.6 | ||
10 | 102 | 97.4 | 101 | 103 | 0.40 | 1.2 | 2.7 | 2.4 | |||
50 | 98.0 | 98.8 | 98.4 | 98.6 | 7.0 | 8.9 | 5.8 | 2.8 | |||
Lincomycin | 0.2 | 102 | 91.9 | 89.7 | 85.8 | 6.2 | 9.9 | 4.1 | 3.3 | ||
2.0 | 97.5 | 91.0 | 94.3 | 90.5 | 5.0 | 3.9 | 5.6 | 0.94 | |||
50 | 83.6 | 76.7 | 77.8 | 95.0 | 1.5 | 5.4 | 10 | 8.6 | |||
Florfenicol | 1.0 | 98.6 | 100 | 101 | 100 | 6.9 | 9.6 | 11 | 10 | ||
2.0 | 102 | 99.1 | 99.5 | 98.3 | 2.5 | 2.07 | 2.90 | 3.3 | |||
100 | 104 | 103 | 101 | 100 | 2.4 | 1.2 | 5.3 | 4.4 | |||
Chloramphenicol | 1.0 | 102 | 107 | 108 | 106 | 3.4 | 2.0 | 1.7 | 0.76 | ||
2.0 | 101 | 99.5 | 103 | 102 | 0.55 | 3.2 | 3.1 | 4.2 | |||
10 | 103 | 101 | 103 | 107 | 5.3 | 3.0 | 4.2 | 2.0 | |||
Erythromycin A | 0.3 | 87.5 | 93.5 | 90.7 | 94.7 | 4.7 | 4.2 | 1.1 | 5.5 | ||
2.0 | 86.4 | 93.9 | 92.1 | 93.7 | 0.88 | 2.1 | 4.2 | 5.2 | |||
40 | 104 | 102 | 100 | 99.7 | 5.5 | 0.8 | 4.2 | 5.6 | |||
Erythromycin A enol ether | 0.3 | 65.3 | 104 | 84.4 | 82.1 | 11 | 4.2 | 15 | 8.1 | ||
2.0 | 76.1 | 97.2 | 71.2 | 90.2 | 13 | 4.2 | 21 | 11 | |||
10 | 86.9 | 99.9 | 83.2 | 90.2 | 14 | 3.9 | 10 | 7.0 | |||
Anhydro erythromycin A | 0.3 | 101 | 86.3 | 98.7 | 94.4 | 2.7 | 5.5 | 9.3 | 6.0 | ||
2.0 | 105 | 94.6 | 96.6 | 98.8 | 0.44 | 12 | 6.2 | 7.4 | |||
10 | 105 | 95.0 | 102 | 108 | 8.8 | 16 | 4.4 | 0.85 |
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