Chinese Journal of Chromatography ›› 2021, Vol. 39 ›› Issue (6): 624-632.DOI: 10.3724/SP.J.1123.2020.12026
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LIANG Sihui1, DAI Hairong1, ZHANG Huayin1, LI Jian2, ZHANG Qiuping2, XU Qian1,3,*(), WANG Chunmin2,*()
Received:
2020-12-24
Online:
2021-06-08
Published:
2021-04-13
Contact:
XU Qian,WANG Chunmin
Supported by:
CLC Number:
LIANG Sihui, DAI Hairong, ZHANG Huayin, LI Jian, ZHANG Qiuping, XU Qian, WANG Chunmin. Determination of tetracycline and fluoroquinolone residues in fish by polydopamine nanofiber mat based solid phase extraction combined with ultra performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Chromatography, 2021, 39(6): 624-632.
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URL: https://www.chrom-china.com/EN/10.3724/SP.J.1123.2020.12026
Compound | tR/min | Precursor ion (m/z) | Product ions (m/z) | Collision energies/V | Cone voltage/V |
---|---|---|---|---|---|
Norfloxacin (NOR) | 1.68 | 320.2 | 302.2*, 276.2, 233.2 | 21, 16, 25 | 31 |
Ciprofloxacin (CIP) | 1.72 | 332.2 | 288.2*, 314.2 | 18, 19 | 31 |
Oxytetracycline (OTC) | 1.74 | 461.3 | 426.3*, 443.3, 201.2 | 19, 13, 37 | 26 |
Enrofloxacin (ENR) | 1.78 | 360.3 | 316.3*, 245.2, 342.1 | 18, 27, 23 | 41 |
Tetracycline (TET) | 1.83 | 445.3 | 410.2*, 154.1 | 18, 27 | 27 |
Chlortetracycline (CTC) | 2.03 | 479.3 | 462.2*, 444.2, 154.1 | 18, 22, 29 | 27 |
Table 1 MS/MS parameters of the six target compounds
Compound | tR/min | Precursor ion (m/z) | Product ions (m/z) | Collision energies/V | Cone voltage/V |
---|---|---|---|---|---|
Norfloxacin (NOR) | 1.68 | 320.2 | 302.2*, 276.2, 233.2 | 21, 16, 25 | 31 |
Ciprofloxacin (CIP) | 1.72 | 332.2 | 288.2*, 314.2 | 18, 19 | 31 |
Oxytetracycline (OTC) | 1.74 | 461.3 | 426.3*, 443.3, 201.2 | 19, 13, 37 | 26 |
Enrofloxacin (ENR) | 1.78 | 360.3 | 316.3*, 245.2, 342.1 | 18, 27, 23 | 41 |
Tetracycline (TET) | 1.83 | 445.3 | 410.2*, 154.1 | 18, 27 | 27 |
Chlortetracycline (CTC) | 2.03 | 479.3 | 462.2*, 444.2, 154.1 | 18, 22, 29 | 27 |
Fig. 4 Effects of (a) mass of adsorbent, (b) ionic strength, (c) flow rates, and (d) eluents on the extraction efficiencies of the six target compounds (n=4)
Compound | Linear range/ (μg/kg) | Linear equation | R2 | LOD/ (μg/kg) | LOQ/ (μg/kg) |
---|---|---|---|---|---|
TET | 2-1000 | y=127.0x+128.2 | 0.9991 | 0.5 | 2.0 |
CTC | 5-1000 | y=120.0x+102.8 | 0.9999 | 1.5 | 5.0 |
OTC | 5-1000 | y=208.5x+29.4 | 0.9993 | 1.5 | 5.0 |
ENR | 5-1000 | y=201.2x+48.6 | 0.9997 | 1.0 | 5.0 |
CIP | 2-1000 | y=144.5x+48.0 | 0.9995 | 0.7 | 2.0 |
NOR | 1-1000 | y=176.8x+25.7 | 0.9998 | 0.3 | 1.0 |
Table 2 Linear ranges, linear equations, coefficient of determination (R2), LODs and LOQs of the six target compounds
Compound | Linear range/ (μg/kg) | Linear equation | R2 | LOD/ (μg/kg) | LOQ/ (μg/kg) |
---|---|---|---|---|---|
TET | 2-1000 | y=127.0x+128.2 | 0.9991 | 0.5 | 2.0 |
CTC | 5-1000 | y=120.0x+102.8 | 0.9999 | 1.5 | 5.0 |
OTC | 5-1000 | y=208.5x+29.4 | 0.9993 | 1.5 | 5.0 |
ENR | 5-1000 | y=201.2x+48.6 | 0.9997 | 1.0 | 5.0 |
CIP | 2-1000 | y=144.5x+48.0 | 0.9995 | 0.7 | 2.0 |
NOR | 1-1000 | y=176.8x+25.7 | 0.9998 | 0.3 | 1.0 |
Compound | Spiked level/ (μg/kg) | Intra-day (n=6)/% | Inter-day (n=4)/% | |||
---|---|---|---|---|---|---|
Recovery±SD | RSD | Recovery±SD | RSD | |||
TET | 2 | 102.13±6.17 | 6.04 | 96.58±8.79 | 9.10 | |
200 | 101.51±4.72 | 4.65 | 98.40±5.18 | 5.26 | ||
1000 | 99.77±2.37 | 2.38 | 100.72±4.49 | 4.46 | ||
CTC | 5 | 98.69±7.84 | 7.94 | 101.93±8.16 | 8.01 | |
200 | 98.94±6.23 | 6.30 | 97.48±5.76 | 5.91 | ||
1000 | 101.24±5.97 | 5.90 | 98.34±4.76 | 4.84 | ||
OTC | 5 | 94.37±7.61 | 8.06 | 97.65±7.37 | 7.55 | |
200 | 95.81±4.92 | 5.14 | 98.46±5.91 | 6.00 | ||
1000 | 98.36±3.52 | 3.58 | 99.04±4.06 | 4.10 | ||
ENR | 5 | 101.63±7.55 | 7.43 | 102.68±7.96 | 7.75 | |
200 | 98.23±7.43 | 7.56 | 94.99±6.08 | 6.40 | ||
1000 | 99.58±4.66 | 4.68 | 96.02±4.97 | 5.18 | ||
CIP | 2 | 101.37±6.88 | 6.79 | 95.27±7.93 | 8.32 | |
200 | 97.28±4.96 | 5.10 | 96.04±5.12 | 5.33 | ||
1000 | 99.79±4.79 | 4.80 | 97.55±4.28 | 4.39 | ||
NOR | 1 | 102.82±6.50 | 6.32 | 95.07±8.35 | 8.78 | |
200 | 98.77±4.35 | 4.40 | 98.13±6.21 | 6.33 | ||
1000 | 100.43±3.96 | 3.94 | 100.24±4.96 | 4.95 |
Table 3 Recoveries and RSDs of the six target compounds in fish
Compound | Spiked level/ (μg/kg) | Intra-day (n=6)/% | Inter-day (n=4)/% | |||
---|---|---|---|---|---|---|
Recovery±SD | RSD | Recovery±SD | RSD | |||
TET | 2 | 102.13±6.17 | 6.04 | 96.58±8.79 | 9.10 | |
200 | 101.51±4.72 | 4.65 | 98.40±5.18 | 5.26 | ||
1000 | 99.77±2.37 | 2.38 | 100.72±4.49 | 4.46 | ||
CTC | 5 | 98.69±7.84 | 7.94 | 101.93±8.16 | 8.01 | |
200 | 98.94±6.23 | 6.30 | 97.48±5.76 | 5.91 | ||
1000 | 101.24±5.97 | 5.90 | 98.34±4.76 | 4.84 | ||
OTC | 5 | 94.37±7.61 | 8.06 | 97.65±7.37 | 7.55 | |
200 | 95.81±4.92 | 5.14 | 98.46±5.91 | 6.00 | ||
1000 | 98.36±3.52 | 3.58 | 99.04±4.06 | 4.10 | ||
ENR | 5 | 101.63±7.55 | 7.43 | 102.68±7.96 | 7.75 | |
200 | 98.23±7.43 | 7.56 | 94.99±6.08 | 6.40 | ||
1000 | 99.58±4.66 | 4.68 | 96.02±4.97 | 5.18 | ||
CIP | 2 | 101.37±6.88 | 6.79 | 95.27±7.93 | 8.32 | |
200 | 97.28±4.96 | 5.10 | 96.04±5.12 | 5.33 | ||
1000 | 99.79±4.79 | 4.80 | 97.55±4.28 | 4.39 | ||
NOR | 1 | 102.82±6.50 | 6.32 | 95.07±8.35 | 8.78 | |
200 | 98.77±4.35 | 4.40 | 98.13±6.21 | 6.33 | ||
1000 | 100.43±3.96 | 3.94 | 100.24±4.96 | 4.95 |
Fig. 6 Extract ion current chromatograms of the six target compounds a. spiked fish sample without SPE (50 μg/kg); b. spiked fish sample after SPE (50 μg/kg); c. standard solution (50 μg/L).
Detection method | Adsorbents | Linear range/ (μg/kg) | LOD/ (μg/kg) | Recovery/% | RSD/% | Ref. | |||
---|---|---|---|---|---|---|---|---|---|
LC-MS/MS | C18 (50 mg) | - | 0.1-10 | 70- | 120 | 2.56- | 17.18 | [ | |
UPLC-MS/MS | C18 (100 mg) | 5- | 100 | 0.1-10 | 80.1- | 124.8 | 0.87- | 20.09 | [ |
UPLC-MS/MS | PSA (200 mg) and C18 (50 mg) | 0.2- | 200 | 0.1-1.6 | 81.6- | 96.6 | 3.6- | 9.2 | [ |
LC-MS/MS | C18 (500 mg) | 5- | 50 | 0.5-5.0 | 47- | 99 | 4- | 17 | [ |
UPLC-MS/MS | PDA-PS NFsM (20 mg) | 1- | 1000 | 0.3-1.5 | 94.37- | 102.82 | 2.38- | 9.10 | this method |
Table 4 Comparison of this proposed method with other methods
Detection method | Adsorbents | Linear range/ (μg/kg) | LOD/ (μg/kg) | Recovery/% | RSD/% | Ref. | |||
---|---|---|---|---|---|---|---|---|---|
LC-MS/MS | C18 (50 mg) | - | 0.1-10 | 70- | 120 | 2.56- | 17.18 | [ | |
UPLC-MS/MS | C18 (100 mg) | 5- | 100 | 0.1-10 | 80.1- | 124.8 | 0.87- | 20.09 | [ |
UPLC-MS/MS | PSA (200 mg) and C18 (50 mg) | 0.2- | 200 | 0.1-1.6 | 81.6- | 96.6 | 3.6- | 9.2 | [ |
LC-MS/MS | C18 (500 mg) | 5- | 50 | 0.5-5.0 | 47- | 99 | 4- | 17 | [ |
UPLC-MS/MS | PDA-PS NFsM (20 mg) | 1- | 1000 | 0.3-1.5 | 94.37- | 102.82 | 2.38- | 9.10 | this method |
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