Chinese Journal of Chromatography ›› 2023, Vol. 41 ›› Issue (3): 274-280.DOI: 10.3724/SP.J.1123.2022.05030
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LIN Qiang1, YANG Chao1, LI Meili1, WANG Jia1, HOU Hanran1, SHAO Bing2, NIU Yumin2,*()
Received:
2022-05-26
Online:
2023-03-08
Published:
2023-03-02
Contact:
NIU Yumin, E-mail:nym0542010@163.com.
Supported by:
CLC Number:
LIN Qiang, YANG Chao, LI Meili, WANG Jia, HOU Hanran, SHAO Bing, NIU Yumin. Determination of 14 paralytic shellfish toxins in plasma and urine by ultra-high performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Chromatography, 2023, 41(3): 274-280.
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URL: https://www.chrom-china.com/EN/10.3724/SP.J.1123.2022.05030
Analyte | Precursor ion (m/z) | Product ions (m/z) | Collision energies/eV | Declustering potential/V | Retention time/min |
---|---|---|---|---|---|
Gonyautoxin 1 (GTX1) | 410.1 | 367.1*, 349.1 | -28, -22 | -100 | 5.66 |
Gonyautoxin 2 (GTX2) | 394.1 | 333.1*, 351.1 | -30, -22 | -130 | 5.74 |
Gonyautoxin 3 (GTX3) | 396.1 | 298.2*, 315.9 | 29, 16 | 50 | 6.60 |
Gonyautoxin 4 (GTX4) | 412.1 | 332.1*, 314.1 | 19, 27 | 20 | 6.57 |
Gonyautoxin 5 (GTX5) | 380.2 | 300.2*, 282.2 | 21, 29 | 20 | 6.76 |
Gonyautoxin 6 (GTX6) | 396.1 | 316.2*, 298.0 | 20, 32 | 30 | 6.94 |
Decarbamoyl-gonyautoxin 2 (DCGTX2) | 353.3 | 255.1*, 273.0 | 27, 13 | 60 | 5.95 |
Decarbamoyl-gonyautoxin 3 (DCGTX3) | 353.3 | 255.1*, 273.0 | 27, 13 | 60 | 6.65 |
N-Sulfocarbamoyl-gonyautoxin 1 (C1) | 473.9 | 122.0*, 333.0 | -30, -43 | -40 | 6.60 |
N-Sulfocarbamoyl-gonyautoxin 2 (C2) | 473.9 | 122.0*, 333.0 | -30, -43 | -40 | 6.93 |
Saxitoxin (STX) | 300.1 | 204.2*, 138.0 | 30, 35 | 140 | 6.68 |
Decarbamoyl-saxitoxin (DCSTX) | 257.1 | 126.3*, 222.3 | 25, 29 | 100 | 6.70 |
Neosaxitoxin (NEO) | 316.1 | 220.1*, 126.1 | 34, 31 | 80 | 6.68 |
Decarbamoyl-neosaxitoxin (DCNEO) | 273.1 | 225.2*, 126.1 | 31, 23 | 30 | 6.68 |
Table 1 MS parameters and retention times of the 14 paralytic shellfish toxins
Analyte | Precursor ion (m/z) | Product ions (m/z) | Collision energies/eV | Declustering potential/V | Retention time/min |
---|---|---|---|---|---|
Gonyautoxin 1 (GTX1) | 410.1 | 367.1*, 349.1 | -28, -22 | -100 | 5.66 |
Gonyautoxin 2 (GTX2) | 394.1 | 333.1*, 351.1 | -30, -22 | -130 | 5.74 |
Gonyautoxin 3 (GTX3) | 396.1 | 298.2*, 315.9 | 29, 16 | 50 | 6.60 |
Gonyautoxin 4 (GTX4) | 412.1 | 332.1*, 314.1 | 19, 27 | 20 | 6.57 |
Gonyautoxin 5 (GTX5) | 380.2 | 300.2*, 282.2 | 21, 29 | 20 | 6.76 |
Gonyautoxin 6 (GTX6) | 396.1 | 316.2*, 298.0 | 20, 32 | 30 | 6.94 |
Decarbamoyl-gonyautoxin 2 (DCGTX2) | 353.3 | 255.1*, 273.0 | 27, 13 | 60 | 5.95 |
Decarbamoyl-gonyautoxin 3 (DCGTX3) | 353.3 | 255.1*, 273.0 | 27, 13 | 60 | 6.65 |
N-Sulfocarbamoyl-gonyautoxin 1 (C1) | 473.9 | 122.0*, 333.0 | -30, -43 | -40 | 6.60 |
N-Sulfocarbamoyl-gonyautoxin 2 (C2) | 473.9 | 122.0*, 333.0 | -30, -43 | -40 | 6.93 |
Saxitoxin (STX) | 300.1 | 204.2*, 138.0 | 30, 35 | 140 | 6.68 |
Decarbamoyl-saxitoxin (DCSTX) | 257.1 | 126.3*, 222.3 | 25, 29 | 100 | 6.70 |
Neosaxitoxin (NEO) | 316.1 | 220.1*, 126.1 | 34, 31 | 80 | 6.68 |
Decarbamoyl-neosaxitoxin (DCNEO) | 273.1 | 225.2*, 126.1 | 31, 23 | 30 | 6.68 |
Fig. 2 Effect of the different solid phase extraction columns on the spiked recoveries (n=6) and the matrix effects of the 14 paralytic shellfish toxins in urine
Fig. 3 Effects of the different ratios of eluent on the spiked recoveries of the 14 paralytic shellfish toxins in urine (n=6) Eluents 1-4 are 50%, 70%, 80% and 90% ACN aqueous solution (containing 0.1% formic acid), respectively.
Analyte | Linear range/(μg/L) | r2 | LODs/(μg/L) | LOQs/(μg/L) | |||
---|---|---|---|---|---|---|---|
Urine | Plasma | Urine | Plasma | ||||
GTX1 | 0.29-36.72 | 0.996 | 1.93 | 0.68 | 5.80 | 2.03 | |
GTX2 | 0.50-63.44 | 0.995 | 3.33 | 1.17 | 10.00 | 3.50 | |
GTX3 | 0.42-26.88 | 0.995 | 2.80 | 0.98 | 8.40 | 2.94 | |
GTX4 | 0.36-11.56 | 0.996 | 2.40 | 0.84 | 7.20 | 2.52 | |
GTX5 | 1.03-32.97 | 0.997 | 6.87 | 2.40 | 20.60 | 7.21 | |
GTX6 | 0.24-7.72 | 0.995 | 1.60 | 0.56 | 4.80 | 1.68 | |
DCGTX2 | 1.72-55.16 | 0.996 | 11.47 | 4.01 | 34.40 | 12.04 | |
DCGTX3 | 0.51-16.25 | 0.997 | 3.33 | 1.17 | 10.00 | 3.50 | |
C1 | 0.66-84.06 | 0.998 | 4.40 | 1.54 | 13.20 | 4.62 | |
C2 | 0.39-25.16 | 0.996 | 2.60 | 0.91 | 7.80 | 2.73 | |
STX | 0.60-38.59 | 0.995 | 4.00 | 1.40 | 12.00 | 4.20 | |
DCSTX | 0.26-33.44 | 0.996 | 1.73 | 0.61 | 5.20 | 1.82 | |
NEO | 0.25-32.05 | 0.997 | 1.67 | 0.58 | 5.00 | 1.75 | |
DCNEO | 0.49-15.78 | 0.996 | 3.27 | 1.14 | 9.80 | 3.43 |
Table 2 Linear ranges, correlation coefficients (r2), LODs and LOQs of the 14 paralytic shellfish toxins
Analyte | Linear range/(μg/L) | r2 | LODs/(μg/L) | LOQs/(μg/L) | |||
---|---|---|---|---|---|---|---|
Urine | Plasma | Urine | Plasma | ||||
GTX1 | 0.29-36.72 | 0.996 | 1.93 | 0.68 | 5.80 | 2.03 | |
GTX2 | 0.50-63.44 | 0.995 | 3.33 | 1.17 | 10.00 | 3.50 | |
GTX3 | 0.42-26.88 | 0.995 | 2.80 | 0.98 | 8.40 | 2.94 | |
GTX4 | 0.36-11.56 | 0.996 | 2.40 | 0.84 | 7.20 | 2.52 | |
GTX5 | 1.03-32.97 | 0.997 | 6.87 | 2.40 | 20.60 | 7.21 | |
GTX6 | 0.24-7.72 | 0.995 | 1.60 | 0.56 | 4.80 | 1.68 | |
DCGTX2 | 1.72-55.16 | 0.996 | 11.47 | 4.01 | 34.40 | 12.04 | |
DCGTX3 | 0.51-16.25 | 0.997 | 3.33 | 1.17 | 10.00 | 3.50 | |
C1 | 0.66-84.06 | 0.998 | 4.40 | 1.54 | 13.20 | 4.62 | |
C2 | 0.39-25.16 | 0.996 | 2.60 | 0.91 | 7.80 | 2.73 | |
STX | 0.60-38.59 | 0.995 | 4.00 | 1.40 | 12.00 | 4.20 | |
DCSTX | 0.26-33.44 | 0.996 | 1.73 | 0.61 | 5.20 | 1.82 | |
NEO | 0.25-32.05 | 0.997 | 1.67 | 0.58 | 5.00 | 1.75 | |
DCNEO | 0.49-15.78 | 0.996 | 3.27 | 1.14 | 9.80 | 3.43 |
Analytes | Matrices | Sample volume/mL | Pre-processing method | LOQs/(μg/L) | Ref. |
---|---|---|---|---|---|
STX, NEO | urine | 0.45 | Online SPE (Oasis WCX exchange columns) | STX: 5.10, NEO: 2.62 | [ |
NEO | plasma | 1.00 | SPE (Enviro-Clean CCX carboxylic acid cation exchange columns) | 0.40 | [ |
STX, NEO | urine | 0.20 | SPE (PA exchange columns) | STX: 1.40, NEO: 1.00 | [ |
14 paralytic shellfish toxins | urine, plasma | 0.20 | urine: liquid-liquid extraction plasma: SPE (PA exchange columns) | urine: 4.80-34.40, plasma: 1.68-12.04 | this research |
Table 3 Comparison of different detection methods
Analytes | Matrices | Sample volume/mL | Pre-processing method | LOQs/(μg/L) | Ref. |
---|---|---|---|---|---|
STX, NEO | urine | 0.45 | Online SPE (Oasis WCX exchange columns) | STX: 5.10, NEO: 2.62 | [ |
NEO | plasma | 1.00 | SPE (Enviro-Clean CCX carboxylic acid cation exchange columns) | 0.40 | [ |
STX, NEO | urine | 0.20 | SPE (PA exchange columns) | STX: 1.40, NEO: 1.00 | [ |
14 paralytic shellfish toxins | urine, plasma | 0.20 | urine: liquid-liquid extraction plasma: SPE (PA exchange columns) | urine: 4.80-34.40, plasma: 1.68-12.04 | this research |
Analyte | Average recoveries/% | Intra-day RSDs/% | Inter-day RSDs/% | |||||||
---|---|---|---|---|---|---|---|---|---|---|
Urine | Plasma | Urine | Plasma | Urine | Plasma | |||||
GTX1 | 83.1-105.6 | 83.3-115.2 | 5.6-15.3 | 7.7-13.6 | 13.5 | 14.1 | ||||
GTX2 | 97.5-12.4 | 79.5-98.0 | 4.5-12.5 | 5.7-15.9 | 5.1 | 14.2 | ||||
GTX3 | 81.3-105.6 | 81.7-115.6 | 3.5-8.9 | 3.6-12.4 | 14.6 | 9.3 | ||||
GTX4 | 86.5-101.8 | 78.6-102.1 | 4.2-12.5 | 8.7-14.5 | 11.5 | 7.7 | ||||
Analyte | Average recoveries/% | Intra-day RSDs/% | Inter-day RSDs/% | |||||||
Urine | Plasma | Urine | Plasma | Urine | Plasma | |||||
GTX5 | 80.6-109.3 | 72.5-110.4 | 3.3-15.6 | 4.5-14.7 | 10.3 | 13.2 | ||||
GTX6 | 85.5-123.4 | 85.7-105.2 | 8.7-16.0 | 5.6-9.6 | 16.0 | 10.4 | ||||
DCGTX2 | 86.7-95.8 | 71.5-97.6 | 4.3-14.0 | 6.3-8.9 | 16.2 | 8.3 | ||||
DCGTX3 | 75.6-91.5 | 75.6-92.0 | 7.9-18.0 | 4.6-14.5 | 13.1 | 13.5 | ||||
C1 | 70.4-93.6 | 71.5-94.3 | 14.2-18.0 | 6.5-11.4 | 10.4 | 15.6 | ||||
C2 | 72.6-104.2 | 75.6-104.5 | 7.7-17.4 | 7.9-10.6 | 10.1 | 5.4 | ||||
STX | 78.9-90.4 | 74.6-91.0 | 5.5-19.1 | 5.8-12.4 | 9.2 | 9.4 | ||||
DCSTX | 77.2-112.4 | 77.4-87.8 | 5.1-14.2 | 3.6-17.8 | 8.3 | 11.1 | ||||
NEO | 76.8-114.6 | 71.4-114.9 | 5.6-12.3 | 5.6-12.3 | 9.0 | 15.2 | ||||
DCNEO | 76.5-11.3 | 76.9-89.7 | 2.3-8.9 | 6.2-14.7 | 5.0 | 4.0 |
Table 4 Recoveries and precisions of the 14 paralytic shellfish toxins (n=6)
Analyte | Average recoveries/% | Intra-day RSDs/% | Inter-day RSDs/% | |||||||
---|---|---|---|---|---|---|---|---|---|---|
Urine | Plasma | Urine | Plasma | Urine | Plasma | |||||
GTX1 | 83.1-105.6 | 83.3-115.2 | 5.6-15.3 | 7.7-13.6 | 13.5 | 14.1 | ||||
GTX2 | 97.5-12.4 | 79.5-98.0 | 4.5-12.5 | 5.7-15.9 | 5.1 | 14.2 | ||||
GTX3 | 81.3-105.6 | 81.7-115.6 | 3.5-8.9 | 3.6-12.4 | 14.6 | 9.3 | ||||
GTX4 | 86.5-101.8 | 78.6-102.1 | 4.2-12.5 | 8.7-14.5 | 11.5 | 7.7 | ||||
Analyte | Average recoveries/% | Intra-day RSDs/% | Inter-day RSDs/% | |||||||
Urine | Plasma | Urine | Plasma | Urine | Plasma | |||||
GTX5 | 80.6-109.3 | 72.5-110.4 | 3.3-15.6 | 4.5-14.7 | 10.3 | 13.2 | ||||
GTX6 | 85.5-123.4 | 85.7-105.2 | 8.7-16.0 | 5.6-9.6 | 16.0 | 10.4 | ||||
DCGTX2 | 86.7-95.8 | 71.5-97.6 | 4.3-14.0 | 6.3-8.9 | 16.2 | 8.3 | ||||
DCGTX3 | 75.6-91.5 | 75.6-92.0 | 7.9-18.0 | 4.6-14.5 | 13.1 | 13.5 | ||||
C1 | 70.4-93.6 | 71.5-94.3 | 14.2-18.0 | 6.5-11.4 | 10.4 | 15.6 | ||||
C2 | 72.6-104.2 | 75.6-104.5 | 7.7-17.4 | 7.9-10.6 | 10.1 | 5.4 | ||||
STX | 78.9-90.4 | 74.6-91.0 | 5.5-19.1 | 5.8-12.4 | 9.2 | 9.4 | ||||
DCSTX | 77.2-112.4 | 77.4-87.8 | 5.1-14.2 | 3.6-17.8 | 8.3 | 11.1 | ||||
NEO | 76.8-114.6 | 71.4-114.9 | 5.6-12.3 | 5.6-12.3 | 9.0 | 15.2 | ||||
DCNEO | 76.5-11.3 | 76.9-89.7 | 2.3-8.9 | 6.2-14.7 | 5.0 | 4.0 |
Analyte | Urine/ (μg/L) | Plasma/ (μg/L) | Analyte | Urine/ (μg/L) | Plasma/ (μg/L) |
---|---|---|---|---|---|
GTX1 | 20.21 | 3.25 | DCGTX3 | 35.26 | 5.62 |
GTX2 | 35.34 | 5.68 | C1 | 41.24 | 10.25 |
GTX3 | 24.78 | 3.12 | C2 | 26.25 | 15.30 |
GTX4 | 26.35 | 5.36 | STX | 30.25 | 10.58 |
GTX5 | 35.62 | 10.25 | DCSTX | 23.54 | 8.96 |
GTX6 | 19.40 | 8.75 | NEO | 24.56 | 10.25 |
DCGTX2 | 55.60 | 13.86 | DCNEO | 36.78 | 15.56 |
Table 5 Concentrations of the 14 paralytic shellfish toxins in plasma and urine samples
Analyte | Urine/ (μg/L) | Plasma/ (μg/L) | Analyte | Urine/ (μg/L) | Plasma/ (μg/L) |
---|---|---|---|---|---|
GTX1 | 20.21 | 3.25 | DCGTX3 | 35.26 | 5.62 |
GTX2 | 35.34 | 5.68 | C1 | 41.24 | 10.25 |
GTX3 | 24.78 | 3.12 | C2 | 26.25 | 15.30 |
GTX4 | 26.35 | 5.36 | STX | 30.25 | 10.58 |
GTX5 | 35.62 | 10.25 | DCSTX | 23.54 | 8.96 |
GTX6 | 19.40 | 8.75 | NEO | 24.56 | 10.25 |
DCGTX2 | 55.60 | 13.86 | DCNEO | 36.78 | 15.56 |
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