色谱 ›› 2023, Vol. 41 ›› Issue (9): 760-770.DOI: 10.3724/SP.J.1123.2022.12010
赵芮1,2, 黄晴雯2, 余智颖3, 韩铮2, 范楷2, 赵志辉2, 聂冬霞1,2,*()
收稿日期:
2022-12-05
出版日期:
2023-09-08
发布日期:
2023-09-15
通讯作者:
*Tel:(021)67131637,E-mail:niedongxia@163.com.
基金资助:
ZHAO Rui1,2, HUANG Qingwen2, YU Zhiying3, HAN Zheng2, FAN Kai2, ZHAO Zhihui2, NIE Dongxia1,2,*()
Received:
2022-12-05
Online:
2023-09-08
Published:
2023-09-15
Supported by:
摘要:
基于QuEChERS-超高效液相色谱-串联质谱法(UPLC-MS/MS),建立了水果(草莓、葡萄、梨和桃)中36种真菌毒素的准确定量分析方法,并应用该方法对不同水果中真菌毒素的污染情况进行了分析。2.0 g样品用10 mL乙酸-乙腈-水(1∶79∶20, v/v/v)提取,无水硫酸镁(2.0 g)和氯化钠(0.5 g)盐析,离心后采用85 mg十八烷基硅烷键合硅胶(C18)和15 mg N-丙基乙二胺(PSA)对上清液进行吸附净化,浓缩复溶后过滤膜;采用Waters XBridge BEH C18色谱柱分离,以5 mmol/L醋酸铵水溶液和甲醇为流动相进行梯度洗脱,采用电喷雾离子源(ESI)正、负离子切换多反应监测模式测定,以空白基质匹配外标曲线法准确定量。结果表明,36种真菌毒素在8.5 min内完成色谱分离,并在各自的线性范围内具有良好的线性关系,相关系数(R2)≥0.990,检出限(LOD)和定量限(LOQ)分别为0.02~5 μg/kg和0.1~10 μg/kg。在低、中、高3个添加水平下,4种水果基质中36种真菌毒素的平均加标回收率为77.0%~118.9%,日内精密度为1.3%~14.9%,日间精密度为0.2%~17.3%。利用所建立的方法对60份水果样品(15份草莓、15份葡萄、15份梨和15份桃)进行检测,共检出11种真菌毒素,平均含量为0.13~35.85 μg/kg,其中3份样品存在多种真菌毒素共同污染的情况。本方法操作简便,快速准确,灵敏度高,重复性与稳定性良好,适用于草莓、葡萄、梨和桃中36种真菌毒素的同时检测。
中图分类号:
赵芮, 黄晴雯, 余智颖, 韩铮, 范楷, 赵志辉, 聂冬霞. QuEChERS-超高效液相色谱-串联质谱法同时测定水果中36种真菌毒素[J]. 色谱, 2023, 41(9): 760-770.
ZHAO Rui, HUANG Qingwen, YU Zhiying, HAN Zheng, FAN Kai, ZHAO Zhihui, NIE Dongxia. Simultaneous determination of 36 mycotoxins in fruits by QuEChERS coupled with ultra performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Chromatography, 2023, 41(9): 760-770.
Mycotoxin | Abbreviation | Retention time/min | Precursor ion (m/z) | Product ions (m/z) | CEs/eV | Ionization mode |
---|---|---|---|---|---|---|
Patulin (展青霉素) | PAT | 1.61 | 152.9 | 109.0*, 81.0 | 12, 14 | - |
Tenuazonic acid (细交链孢菌酮酸) | TeA | 1.77 | 198.1 | 125.0*, 153.1 | 16, 12 | + |
Deoxynevalenol (脱氧雪腐镰刀菌烯醇) | DON | 1.96 | 297.1 | 249.1*, 203.1 | 12, 14 | + |
Altenusin (细格菌素) | ALS | 2.52 | 289.0 | 230.1*, 245.0 | 20, 17 | - |
Aflatoxin M2 (黄曲霉毒素M2) | AFM2 | 3.01 | 331.2 | 285.0*, 241.1 | 24, 42 | + |
15-Acetyl-deoxynivalenol (15-乙酰基-脱氧雪腐镰刀菌烯醇) | 15-ADON | 3.04 | 356.0 | 339.0*, 321.0 | 6, 12 | + |
3-Acetyl-deoxynivalenol (3-乙酰基-脱氧雪腐镰刀菌烯醇) | 3-ADON | 3.05 | 339.0 | 231.0*, 203.0 | 16, 16 | + |
Aflatoxin G2 (黄曲霉毒素G2) | AFG2 | 3.24 | 331.2 | 245.1*, 189.1 | 40, 30 | + |
Aflatoxin M1 (黄曲霉毒素M1) | AFM1 | 3.27 | 329.2 | 273.1*, 229.2 | 22, 38 | + |
Aflatoxin G1 (黄曲霉毒素G1) | AFG1 | 3.45 | 329.2 | 243.1*, 199.9 | 26, 42 | + |
Aflatoxin B2 (黄曲霉毒素B2) | AFB2 | 3.67 | 315.2 | 287.1*, 259.1 | 26, 28 | + |
Ochratoxin B (赭曲霉毒素B) | OTB | 3.74 | 370.2 | 205.1*, 187.1 | 20, 34 | + |
Mycophenolic acid (麦考酚酸) | MPA | 3.85 | 321.3 | 207.1*, 159.1 | 34, 20 | + |
Aflatoxin B1 (黄曲霉毒素B1) | AFB1 | 3.86 | 313.2 | 241.2*, 285.0 | 36, 22 | + |
Altenuene (交链孢霉烯) | ALT | 3.92 | 293.0 | 257.1*, 275.1 | 14, 8 | + |
Diacetoxyscirpenol (蛇形毒素) | DAS | 4.00 | 384.4 | 307.2*, 247.2 | 12, 10 | + |
Citrinin (桔青霉素) | CIT | 4.00 | 251.0 | 233.1*, 205.1 | 16, 26 | + |
Ochratoxin A (赭曲霉毒素A) | OTA | 4.36 | 404.3 | 239.0*, 221.0 | 22, 34 | + |
Alternariol (链格孢酚) | AOH | 4.56 | 259.0 | 185.1*, 213.1 | 28, 24 | + |
HT-2 toxin (HT2毒素) | HT2 | 4.66 | 442.4 | 215.2*, 263.2 | 10, 10 | + |
β-Zearalanol (β-玉米赤霉醇) | β-ZAL | 4.72 | 321.3 | 259.2*, 107.1 | 24, 36 | - |
Tentoxin (腾毒素) | Ten | 4.82 | 415.2 | 312.2*, 199.2 | 18, 12 | + |
β-Zearalenol (β-玉米赤霉烯醇) | β-ZOL | 4.88 | 319.3 | 160.0*, 174.2 | 26, 26 | - |
T-2 toxin (T2毒素) | T2 | 5.06 | 484.4 | 185.1*, 305.2 | 18, 14 | + |
α-Zearalanol (α-玉米赤霉醇) | α-ZAL | 5.14 | 321.3 | 259.2*, 107.1 | 24, 36 | - |
α-Zearalenol (α-玉米赤霉烯醇) | α-ZOL | 5.24 | 319.3 | 160.0*, 174.2 | 26, 26 | - |
Zearalanone (玉米赤霉酮) | ZAN | 5.33 | 319.0 | 205.0*, 161.0 | 24, 24 | - |
Zearalenone (玉米赤霉烯酮) | ZEN | 5.41 | 317.2 | 175.0*, 131.0 | 24, 26 | - |
Sterigmatocystin (杂色去霉素) | SMC | 5.59 | 325.2 | 310.1*, 253.1 | 72, 72 | + |
Alternariol-methyl ether (交链孢霉甲基醚) | AME | 5.73 | 273.0 | 258.0*, 128.1 | 25, 26 | + |
Ochratoxin C (赭曲霉毒素C) | OTC | 5.75 | 432.1 | 239.0*, 358.1 | 24, 14 | + |
Enniatin B (恩镰孢菌素B) | ENNB | 6.52 | 640.4 | 196.2*, 527.1 | 25, 22 | + |
Beauvericin (白僵菌素) | BEA | 6.64 | 784.4 | 134.1*, 244.2 | 56, 30 | + |
Enniatin B1 (恩镰孢菌素B1) | ENNB1 | 6.70 | 655.6 | 196.0*, 210.0 | 23, 25 | + |
Enniatin A1 (恩镰孢菌素A1) | ENNA1 | 6.89 | 669.6 | 210.0*, 100.1 | 25, 40 | + |
Enniatin A (恩镰孢菌素A) | ENNA | 7.10 | 682.5 | 210.4*, 328.1 | 25, 30 | + |
表 1 36种真菌毒素的质谱参数
Table 1 MS parameters for the 36 mycotoxins
Mycotoxin | Abbreviation | Retention time/min | Precursor ion (m/z) | Product ions (m/z) | CEs/eV | Ionization mode |
---|---|---|---|---|---|---|
Patulin (展青霉素) | PAT | 1.61 | 152.9 | 109.0*, 81.0 | 12, 14 | - |
Tenuazonic acid (细交链孢菌酮酸) | TeA | 1.77 | 198.1 | 125.0*, 153.1 | 16, 12 | + |
Deoxynevalenol (脱氧雪腐镰刀菌烯醇) | DON | 1.96 | 297.1 | 249.1*, 203.1 | 12, 14 | + |
Altenusin (细格菌素) | ALS | 2.52 | 289.0 | 230.1*, 245.0 | 20, 17 | - |
Aflatoxin M2 (黄曲霉毒素M2) | AFM2 | 3.01 | 331.2 | 285.0*, 241.1 | 24, 42 | + |
15-Acetyl-deoxynivalenol (15-乙酰基-脱氧雪腐镰刀菌烯醇) | 15-ADON | 3.04 | 356.0 | 339.0*, 321.0 | 6, 12 | + |
3-Acetyl-deoxynivalenol (3-乙酰基-脱氧雪腐镰刀菌烯醇) | 3-ADON | 3.05 | 339.0 | 231.0*, 203.0 | 16, 16 | + |
Aflatoxin G2 (黄曲霉毒素G2) | AFG2 | 3.24 | 331.2 | 245.1*, 189.1 | 40, 30 | + |
Aflatoxin M1 (黄曲霉毒素M1) | AFM1 | 3.27 | 329.2 | 273.1*, 229.2 | 22, 38 | + |
Aflatoxin G1 (黄曲霉毒素G1) | AFG1 | 3.45 | 329.2 | 243.1*, 199.9 | 26, 42 | + |
Aflatoxin B2 (黄曲霉毒素B2) | AFB2 | 3.67 | 315.2 | 287.1*, 259.1 | 26, 28 | + |
Ochratoxin B (赭曲霉毒素B) | OTB | 3.74 | 370.2 | 205.1*, 187.1 | 20, 34 | + |
Mycophenolic acid (麦考酚酸) | MPA | 3.85 | 321.3 | 207.1*, 159.1 | 34, 20 | + |
Aflatoxin B1 (黄曲霉毒素B1) | AFB1 | 3.86 | 313.2 | 241.2*, 285.0 | 36, 22 | + |
Altenuene (交链孢霉烯) | ALT | 3.92 | 293.0 | 257.1*, 275.1 | 14, 8 | + |
Diacetoxyscirpenol (蛇形毒素) | DAS | 4.00 | 384.4 | 307.2*, 247.2 | 12, 10 | + |
Citrinin (桔青霉素) | CIT | 4.00 | 251.0 | 233.1*, 205.1 | 16, 26 | + |
Ochratoxin A (赭曲霉毒素A) | OTA | 4.36 | 404.3 | 239.0*, 221.0 | 22, 34 | + |
Alternariol (链格孢酚) | AOH | 4.56 | 259.0 | 185.1*, 213.1 | 28, 24 | + |
HT-2 toxin (HT2毒素) | HT2 | 4.66 | 442.4 | 215.2*, 263.2 | 10, 10 | + |
β-Zearalanol (β-玉米赤霉醇) | β-ZAL | 4.72 | 321.3 | 259.2*, 107.1 | 24, 36 | - |
Tentoxin (腾毒素) | Ten | 4.82 | 415.2 | 312.2*, 199.2 | 18, 12 | + |
β-Zearalenol (β-玉米赤霉烯醇) | β-ZOL | 4.88 | 319.3 | 160.0*, 174.2 | 26, 26 | - |
T-2 toxin (T2毒素) | T2 | 5.06 | 484.4 | 185.1*, 305.2 | 18, 14 | + |
α-Zearalanol (α-玉米赤霉醇) | α-ZAL | 5.14 | 321.3 | 259.2*, 107.1 | 24, 36 | - |
α-Zearalenol (α-玉米赤霉烯醇) | α-ZOL | 5.24 | 319.3 | 160.0*, 174.2 | 26, 26 | - |
Zearalanone (玉米赤霉酮) | ZAN | 5.33 | 319.0 | 205.0*, 161.0 | 24, 24 | - |
Zearalenone (玉米赤霉烯酮) | ZEN | 5.41 | 317.2 | 175.0*, 131.0 | 24, 26 | - |
Sterigmatocystin (杂色去霉素) | SMC | 5.59 | 325.2 | 310.1*, 253.1 | 72, 72 | + |
Alternariol-methyl ether (交链孢霉甲基醚) | AME | 5.73 | 273.0 | 258.0*, 128.1 | 25, 26 | + |
Ochratoxin C (赭曲霉毒素C) | OTC | 5.75 | 432.1 | 239.0*, 358.1 | 24, 14 | + |
Enniatin B (恩镰孢菌素B) | ENNB | 6.52 | 640.4 | 196.2*, 527.1 | 25, 22 | + |
Beauvericin (白僵菌素) | BEA | 6.64 | 784.4 | 134.1*, 244.2 | 56, 30 | + |
Enniatin B1 (恩镰孢菌素B1) | ENNB1 | 6.70 | 655.6 | 196.0*, 210.0 | 23, 25 | + |
Enniatin A1 (恩镰孢菌素A1) | ENNA1 | 6.89 | 669.6 | 210.0*, 100.1 | 25, 40 | + |
Enniatin A (恩镰孢菌素A) | ENNA | 7.10 | 682.5 | 210.4*, 328.1 | 25, 30 | + |
图 1 36种真菌毒素混合标准工作液(100 μg/L)的MRM色谱图
Fig. 1 Multiple reaction monitoring (MRM) chromatograms of the 36 mycotoxins (100 μg/L) in mixed standard solutions
Mycotoxin | Strawberry | Grape | Pear | Peach | ||||||||||||||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Linear range | LOD | LOQ | Linear range | LOD | LOQ | Linear range | LOD | LOQ | Linear range | LOD | LOQ | |||||||||||||||
PAT | 10- | 200 | 0.990 | 5 | 10 | 10- | 200 | 0.994 | 5 | 10 | 5- | 200 | 0.998 | 2 | 5 | 2- | 200 | 0.996 | 1 | 2 | ||||||
TeA | 5- | 200 | 0.999 | 2 | 5 | 2- | 200 | 0.997 | 1 | 2 | 5- | 200 | 0.997 | 2 | 5 | 0.5- | 200 | 0.998 | 0.2 | 0.5 | ||||||
DON | 5- | 200 | 0.999 | 2 | 5 | 5- | 200 | 0.997 | 2 | 5 | 5- | 200 | 0.992 | 2 | 5 | 5- | 200 | 0.994 | 2 | 5 | ||||||
ALS | 5- | 200 | 0.999 | 2 | 5 | 0.1- | 200 | 0.991 | 0.05 | 0.1 | 5- | 200 | 0.998 | 2 | 5 | 1- | 100 | 0.990 | 0.5 | 1 | ||||||
AFM2 | 0.5- | 200 | 0.998 | 0.2 | 0.5 | 0.5- | 200 | 0.996 | 0.2 | 0.5 | 2- | 200 | 0.997 | 1 | 2 | 0.1- | 200 | 0.995 | 0.04 | 0.1 | ||||||
15-ADON | 5- | 200 | 0.998 | 3 | 5 | 1- | 200 | 0.996 | 0.5 | 1 | 5- | 200 | 0.993 | 2 | 5 | 5- | 200 | 0.995 | 3 | 5 | ||||||
3-ADON | 2- | 200 | 0.999 | 1 | 2 | 1- | 200 | 0.996 | 0.6 | 1 | 5- | 200 | 0.996 | 2 | 5 | 2- | 200 | 0.999 | 1 | 2 | ||||||
AFG2 | 0.5- | 200 | 0.996 | 0.1 | 0.5 | 0.5- | 200 | 0.997 | 0.3 | 0.5 | 1- | 200 | 0.997 | 0.5 | 1 | 0.5- | 200 | 0.998 | 0.3 | 0.5 | ||||||
AFM1 | 0.5- | 200 | 0.995 | 0.3 | 0.5 | 0.2- | 200 | 0.994 | 0.1 | 0.2 | 1- | 200 | 0.993 | 0.5 | 1 | 0.5- | 200 | 0.994 | 0.3 | 0.5 | ||||||
AFG1 | 0.5- | 200 | 0.999 | 0.2 | 0.5 | 0.1- | 200 | 0.999 | 0.05 | 0.1 | 1- | 200 | 0.993 | 0.4 | 1 | 0.5- | 200 | 0.998 | 0.2 | 0.5 | ||||||
AFB2 | 0.1- | 200 | 0.999 | 0.02 | 0.1 | 0.1- | 200 | 0.999 | 0.05 | 0.1 | 1- | 200 | 0.995 | 0.5 | 1 | 0.1- | 200 | 0.995 | 0.05 | 0.1 | ||||||
AFB1 | 0.1- | 200 | 0.992 | 0.05 | 0.1 | 0.2- | 200 | 0.998 | 0.1 | 0.2 | 1- | 200 | 0.992 | 0.5 | 1 | 0.1- | 200 | 0.994 | 0.05 | 0.1 | ||||||
OTB | 0.1- | 200 | 0.999 | 0.05 | 0.1 | 1- | 200 | 0.999 | 0.5 | 1 | 1- | 200 | 0.998 | 0.5 | 1 | 1- | 200 | 0.999 | 0.5 | 1 | ||||||
MPA | 0.2- | 200 | 0.995 | 0.05 | 0.2 | 0.2- | 200 | 0.999 | 0.1 | 0.2 | 0.5- | 200 | 0.997 | 0.3 | 0.5 | 0.5- | 200 | 0.997 | 0.2 | 0.5 | ||||||
ALT | 1- | 200 | 0.999 | 0.5 | 1 | 0.5- | 200 | 0.992 | 0.2 | 0.5 | 5- | 200 | 0.994 | 3 | 5 | 2- | 200 | 0.994 | 1 | 2 | ||||||
DAS | 0.1- | 200 | 0.999 | 0.05 | 0.1 | 0.1- | 200 | 0.996 | 0.05 | 0.1 | 0.5- | 200 | 0.999 | 0.3 | 0.5 | 0.2- | 200 | 0.999 | 0.1 | 0.2 | ||||||
CIT | 2- | 200 | 0.999 | 1 | 2 | 1- | 200 | 0.999 | 0.5 | 1 | 1- | 200 | 0.996 | 0.5 | 1 | 2- | 200 | 0.998 | 1 | 2 | ||||||
OTA | 0.1- | 200 | 0.999 | 0.02 | 0.1 | 0.1- | 200 | 0.999 | 0.05 | 0.1 | 0.2- | 200 | 0.998 | 0.1 | 0.2 | 0.1- | 200 | 0.998 | 0.05 | 0.1 | ||||||
AOH | 1- | 200 | 0.999 | 0.2 | 1 | 2- | 100 | 0.991 | 1 | 2 | 2- | 200 | 0.996 | 2 | 5 | 2- | 200 | 0.993 | 1 | 2 | ||||||
HT2 | 2- | 200 | 0.999 | 1 | 2 | 2- | 200 | 0.997 | 1 | 2 | 2- | 200 | 0.999 | 1 | 2 | 1- | 200 | 0.998 | 0.5 | 1 | ||||||
β-ZAL | 1- | 200 | 0.996 | 0.5 | 1 | 0.5- | 200 | 0.999 | 0.3 | 0.5 | 1- | 200 | 0.994 | 0.5 | 1 | 1- | 200 | 0.996 | 0.6 | 1 | ||||||
Ten | 0.1- | 200 | 0.998 | 0.05 | 0.1 | 0.5- | 200 | 0.991 | 0.3 | 0.5 | 0.5- | 200 | 0.997 | 0.2 | 0.5 | 0.5- | 200 | 0.996 | 0.2 | 0.5 | ||||||
β-ZOL | 0.5- | 200 | 0.999 | 0.2 | 0.5 | 0.5- | 200 | 0.997 | 0.2 | 0.5 | 1- | 100 | 0.995 | 0.6 | 1 | 1- | 200 | 0.992 | 0.4 | 1 | ||||||
T2 | 0.1- | 200 | 0.998 | 0.05 | 0.1 | 0.5- | 200 | 0.991 | 0.3 | 0.5 | 0.1- | 200 | 0.993 | 0.05 | 0.1 | 0.2- | 200 | 0.998 | 0.1 | 0.2 | ||||||
α-ZAL | 1- | 200 | 0.998 | 0.5 | 1 | 0.5- | 50 | 0.999 | 0.2 | 0.5 | 2- | 200 | 0.991 | 1 | 2 | 1- | 200 | 0.992 | 0.6 | 1 | ||||||
α-ZOL | 0.5- | 200 | 0.999 | 0.2 | 0.5 | 0.5- | 50 | 0.998 | 0.2 | 0.5 | 1- | 100 | 0.991 | 0.5 | 1 | 1- | 100 | 0.997 | 0.5 | 1 | ||||||
ZAN | 0.5- | 200 | 0.997 | 0.2 | 0.5 | 0.5- | 50 | 0.996 | 0.2 | 0.5 | 0.2- | 100 | 0.992 | 0.1 | 0.2 | 1- | 100 | 0.996 | 0.5 | 1 | ||||||
ZEN | 1- | 200 | 0.996 | 0.5 | 1 | 0.1- | 50 | 0.997 | 0.05 | 0.1 | 0.5- | 200 | 0.991 | 0.2 | 0.5 | 1- | 100 | 0.995 | 0.5 | 1 | ||||||
SMC | 0.1- | 50 | 0.999 | 0.05 | 0.1 | 1- | 200 | 0.994 | 0.5 | 1 | 0.1- | 100 | 0.997 | 0.05 | 0.1 | 0.5- | 100 | 0.993 | 0.2 | 0.5 | ||||||
AME | 1- | 200 | 0.999 | 0.5 | 1 | 2- | 100 | 0.990 | 1 | 2 | 5- | 200 | 0.990 | 3 | 5 | 1- | 200 | 0.991 | 0.5 | 1 | ||||||
OTC | 0.1- | 100 | 0.995 | 0.05 | 0.1 | 0.5- | 50 | 0.997 | 0.2 | 0.5 | 0.2- | 100 | 0.993 | 0.1 | 0.2 | 1- | 200 | 0.994 | 0.5 | 1 | ||||||
ENNB | 0.1- | 200 | 0.999 | 0.05 | 0.1 | 0.1- | 50 | 0.996 | 0.04 | 0.1 | 0.5- | 100 | 0.992 | 0.2 | 0.5 | 1- | 200 | 0.992 | 0.5 | 1 | ||||||
BEA | 0.1- | 200 | 0.996 | 0.05 | 0.1 | 1- | 200 | 0.993 | 0.5 | 1 | 2- | 200 | 0.998 | 1 | 2 | 0.1- | 200 | 0.992 | 0.05 | 0.1 | ||||||
ENNB1 | 0.1- | 200 | 0.999 | 0.05 | 0.1 | 0.1- | 50 | 0.998 | 0.05 | 0.1 | 0.5- | 100 | 0.991 | 0.2 | 0.5 | 0.1- | 200 | 0.992 | 0.05 | 0.1 | ||||||
ENNA1 | 0.1- | 200 | 0.999 | 0.02 | 0.1 | 0.1- | 50 | 0.995 | 0.05 | 0.1 | 1- | 100 | 0.992 | 0.5 | 1 | 0.1- | 200 | 0.992 | 0.05 | 0.1 | ||||||
ENNA | 0.1- | 200 | 0.999 | 0.05 | 0.1 | 0.2- | 50 | 0.997 | 0.1 | 0.2 | 1- | 100 | 0.991 | 0.5 | 1 | 0.1- | 200 | 0.992 | 0.06 | 0.1 |
表 2 36种真菌毒素在4种水果基质中的线性范围、相关系数、检出限和定量限
Table 2 Linear ranges, correlation coefficients (R2), limits of detection (LODs)and limits of quantification (LOQs) of the 36 mycotoxins in four fruit matrices μg/kg
Mycotoxin | Strawberry | Grape | Pear | Peach | ||||||||||||||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Linear range | LOD | LOQ | Linear range | LOD | LOQ | Linear range | LOD | LOQ | Linear range | LOD | LOQ | |||||||||||||||
PAT | 10- | 200 | 0.990 | 5 | 10 | 10- | 200 | 0.994 | 5 | 10 | 5- | 200 | 0.998 | 2 | 5 | 2- | 200 | 0.996 | 1 | 2 | ||||||
TeA | 5- | 200 | 0.999 | 2 | 5 | 2- | 200 | 0.997 | 1 | 2 | 5- | 200 | 0.997 | 2 | 5 | 0.5- | 200 | 0.998 | 0.2 | 0.5 | ||||||
DON | 5- | 200 | 0.999 | 2 | 5 | 5- | 200 | 0.997 | 2 | 5 | 5- | 200 | 0.992 | 2 | 5 | 5- | 200 | 0.994 | 2 | 5 | ||||||
ALS | 5- | 200 | 0.999 | 2 | 5 | 0.1- | 200 | 0.991 | 0.05 | 0.1 | 5- | 200 | 0.998 | 2 | 5 | 1- | 100 | 0.990 | 0.5 | 1 | ||||||
AFM2 | 0.5- | 200 | 0.998 | 0.2 | 0.5 | 0.5- | 200 | 0.996 | 0.2 | 0.5 | 2- | 200 | 0.997 | 1 | 2 | 0.1- | 200 | 0.995 | 0.04 | 0.1 | ||||||
15-ADON | 5- | 200 | 0.998 | 3 | 5 | 1- | 200 | 0.996 | 0.5 | 1 | 5- | 200 | 0.993 | 2 | 5 | 5- | 200 | 0.995 | 3 | 5 | ||||||
3-ADON | 2- | 200 | 0.999 | 1 | 2 | 1- | 200 | 0.996 | 0.6 | 1 | 5- | 200 | 0.996 | 2 | 5 | 2- | 200 | 0.999 | 1 | 2 | ||||||
AFG2 | 0.5- | 200 | 0.996 | 0.1 | 0.5 | 0.5- | 200 | 0.997 | 0.3 | 0.5 | 1- | 200 | 0.997 | 0.5 | 1 | 0.5- | 200 | 0.998 | 0.3 | 0.5 | ||||||
AFM1 | 0.5- | 200 | 0.995 | 0.3 | 0.5 | 0.2- | 200 | 0.994 | 0.1 | 0.2 | 1- | 200 | 0.993 | 0.5 | 1 | 0.5- | 200 | 0.994 | 0.3 | 0.5 | ||||||
AFG1 | 0.5- | 200 | 0.999 | 0.2 | 0.5 | 0.1- | 200 | 0.999 | 0.05 | 0.1 | 1- | 200 | 0.993 | 0.4 | 1 | 0.5- | 200 | 0.998 | 0.2 | 0.5 | ||||||
AFB2 | 0.1- | 200 | 0.999 | 0.02 | 0.1 | 0.1- | 200 | 0.999 | 0.05 | 0.1 | 1- | 200 | 0.995 | 0.5 | 1 | 0.1- | 200 | 0.995 | 0.05 | 0.1 | ||||||
AFB1 | 0.1- | 200 | 0.992 | 0.05 | 0.1 | 0.2- | 200 | 0.998 | 0.1 | 0.2 | 1- | 200 | 0.992 | 0.5 | 1 | 0.1- | 200 | 0.994 | 0.05 | 0.1 | ||||||
OTB | 0.1- | 200 | 0.999 | 0.05 | 0.1 | 1- | 200 | 0.999 | 0.5 | 1 | 1- | 200 | 0.998 | 0.5 | 1 | 1- | 200 | 0.999 | 0.5 | 1 | ||||||
MPA | 0.2- | 200 | 0.995 | 0.05 | 0.2 | 0.2- | 200 | 0.999 | 0.1 | 0.2 | 0.5- | 200 | 0.997 | 0.3 | 0.5 | 0.5- | 200 | 0.997 | 0.2 | 0.5 | ||||||
ALT | 1- | 200 | 0.999 | 0.5 | 1 | 0.5- | 200 | 0.992 | 0.2 | 0.5 | 5- | 200 | 0.994 | 3 | 5 | 2- | 200 | 0.994 | 1 | 2 | ||||||
DAS | 0.1- | 200 | 0.999 | 0.05 | 0.1 | 0.1- | 200 | 0.996 | 0.05 | 0.1 | 0.5- | 200 | 0.999 | 0.3 | 0.5 | 0.2- | 200 | 0.999 | 0.1 | 0.2 | ||||||
CIT | 2- | 200 | 0.999 | 1 | 2 | 1- | 200 | 0.999 | 0.5 | 1 | 1- | 200 | 0.996 | 0.5 | 1 | 2- | 200 | 0.998 | 1 | 2 | ||||||
OTA | 0.1- | 200 | 0.999 | 0.02 | 0.1 | 0.1- | 200 | 0.999 | 0.05 | 0.1 | 0.2- | 200 | 0.998 | 0.1 | 0.2 | 0.1- | 200 | 0.998 | 0.05 | 0.1 | ||||||
AOH | 1- | 200 | 0.999 | 0.2 | 1 | 2- | 100 | 0.991 | 1 | 2 | 2- | 200 | 0.996 | 2 | 5 | 2- | 200 | 0.993 | 1 | 2 | ||||||
HT2 | 2- | 200 | 0.999 | 1 | 2 | 2- | 200 | 0.997 | 1 | 2 | 2- | 200 | 0.999 | 1 | 2 | 1- | 200 | 0.998 | 0.5 | 1 | ||||||
β-ZAL | 1- | 200 | 0.996 | 0.5 | 1 | 0.5- | 200 | 0.999 | 0.3 | 0.5 | 1- | 200 | 0.994 | 0.5 | 1 | 1- | 200 | 0.996 | 0.6 | 1 | ||||||
Ten | 0.1- | 200 | 0.998 | 0.05 | 0.1 | 0.5- | 200 | 0.991 | 0.3 | 0.5 | 0.5- | 200 | 0.997 | 0.2 | 0.5 | 0.5- | 200 | 0.996 | 0.2 | 0.5 | ||||||
β-ZOL | 0.5- | 200 | 0.999 | 0.2 | 0.5 | 0.5- | 200 | 0.997 | 0.2 | 0.5 | 1- | 100 | 0.995 | 0.6 | 1 | 1- | 200 | 0.992 | 0.4 | 1 | ||||||
T2 | 0.1- | 200 | 0.998 | 0.05 | 0.1 | 0.5- | 200 | 0.991 | 0.3 | 0.5 | 0.1- | 200 | 0.993 | 0.05 | 0.1 | 0.2- | 200 | 0.998 | 0.1 | 0.2 | ||||||
α-ZAL | 1- | 200 | 0.998 | 0.5 | 1 | 0.5- | 50 | 0.999 | 0.2 | 0.5 | 2- | 200 | 0.991 | 1 | 2 | 1- | 200 | 0.992 | 0.6 | 1 | ||||||
α-ZOL | 0.5- | 200 | 0.999 | 0.2 | 0.5 | 0.5- | 50 | 0.998 | 0.2 | 0.5 | 1- | 100 | 0.991 | 0.5 | 1 | 1- | 100 | 0.997 | 0.5 | 1 | ||||||
ZAN | 0.5- | 200 | 0.997 | 0.2 | 0.5 | 0.5- | 50 | 0.996 | 0.2 | 0.5 | 0.2- | 100 | 0.992 | 0.1 | 0.2 | 1- | 100 | 0.996 | 0.5 | 1 | ||||||
ZEN | 1- | 200 | 0.996 | 0.5 | 1 | 0.1- | 50 | 0.997 | 0.05 | 0.1 | 0.5- | 200 | 0.991 | 0.2 | 0.5 | 1- | 100 | 0.995 | 0.5 | 1 | ||||||
SMC | 0.1- | 50 | 0.999 | 0.05 | 0.1 | 1- | 200 | 0.994 | 0.5 | 1 | 0.1- | 100 | 0.997 | 0.05 | 0.1 | 0.5- | 100 | 0.993 | 0.2 | 0.5 | ||||||
AME | 1- | 200 | 0.999 | 0.5 | 1 | 2- | 100 | 0.990 | 1 | 2 | 5- | 200 | 0.990 | 3 | 5 | 1- | 200 | 0.991 | 0.5 | 1 | ||||||
OTC | 0.1- | 100 | 0.995 | 0.05 | 0.1 | 0.5- | 50 | 0.997 | 0.2 | 0.5 | 0.2- | 100 | 0.993 | 0.1 | 0.2 | 1- | 200 | 0.994 | 0.5 | 1 | ||||||
ENNB | 0.1- | 200 | 0.999 | 0.05 | 0.1 | 0.1- | 50 | 0.996 | 0.04 | 0.1 | 0.5- | 100 | 0.992 | 0.2 | 0.5 | 1- | 200 | 0.992 | 0.5 | 1 | ||||||
BEA | 0.1- | 200 | 0.996 | 0.05 | 0.1 | 1- | 200 | 0.993 | 0.5 | 1 | 2- | 200 | 0.998 | 1 | 2 | 0.1- | 200 | 0.992 | 0.05 | 0.1 | ||||||
ENNB1 | 0.1- | 200 | 0.999 | 0.05 | 0.1 | 0.1- | 50 | 0.998 | 0.05 | 0.1 | 0.5- | 100 | 0.991 | 0.2 | 0.5 | 0.1- | 200 | 0.992 | 0.05 | 0.1 | ||||||
ENNA1 | 0.1- | 200 | 0.999 | 0.02 | 0.1 | 0.1- | 50 | 0.995 | 0.05 | 0.1 | 1- | 100 | 0.992 | 0.5 | 1 | 0.1- | 200 | 0.992 | 0.05 | 0.1 | ||||||
ENNA | 0.1- | 200 | 0.999 | 0.05 | 0.1 | 0.2- | 50 | 0.997 | 0.1 | 0.2 | 1- | 100 | 0.991 | 0.5 | 1 | 0.1- | 200 | 0.992 | 0.06 | 0.1 |
Samples | Numbers of myco- toxins | Extraction solvents | Purification materials | Mobile phases | Linear range/ (μg/kg) | LODs and LOQs/ (μg/kg) | Ref. |
---|---|---|---|---|---|---|---|
Maize | 20 | acetonitrile-water-formic acid (80∶18∶2, v/v/v) | 300 mg magnesium sulfate, 150 mg PSA and 150 mg C18 | 0.1% formic acid aqueous solution, methanol | 0.25-200 | 0.17-6.67, 0.5-20 | [ |
Nutmeg | 21 | acetonitrile-water-formic acid (84∶15∶1, v/v/v) | 100 mg C18 and 200 mg magnesium sulfate | 0.1% formic acid methanol, 2 mmol/L ammonium formate aqueous solution | 0.125-1000 | 0.04-3.5, 0.125-10 | [ |
Tea | 6 | acetonitrile-water-acetic acid (79∶20∶1, v/v/v) | 150 mg C18 and 150 mg PSA | 5 mmol/L ammonium formate aqueous solution, 5 mmol/L ammonium formate methanol | - | 1, 1 | [ |
Ketchup | 5 | acetonitrile, water | 0.5 g magnesium sulfate and 100 mg C18 | 0.1% formic acid aqueous solution, acetonitrile | 0.5-200 | 1, 2.5 | [ |
Nut | 20 | acetonitrile | 0.2 g C18 | acetonitrile, 0.05% formic acid aqueous solution | 1-500 | 0.03-2.25, 0.11-7.50 | [ |
Tomato | 9 | acetonitrile-water-formic acid (84∶15∶1, v/v/v) | 200 mg C18 | 5 mmol/L ammonium acetate aqueous solution, methanol | 1-200 | 0.3-1.5, 1-10 | [ |
Fruits | 36 | acetic acid-acetonitrile- water (1∶79∶20, v/v/v) | 85 mg C18 and 15 mg PSA | 5 mmol/L ammonium acetate aqueous solution, methanol | 0.1-200 | 0.02-5, 0.1-10 | this study |
表 3 与已报道文献中真菌毒素检测方法的比较
Table 3 Comparisons with previously developed methods for the determination of mycotoxins
Samples | Numbers of myco- toxins | Extraction solvents | Purification materials | Mobile phases | Linear range/ (μg/kg) | LODs and LOQs/ (μg/kg) | Ref. |
---|---|---|---|---|---|---|---|
Maize | 20 | acetonitrile-water-formic acid (80∶18∶2, v/v/v) | 300 mg magnesium sulfate, 150 mg PSA and 150 mg C18 | 0.1% formic acid aqueous solution, methanol | 0.25-200 | 0.17-6.67, 0.5-20 | [ |
Nutmeg | 21 | acetonitrile-water-formic acid (84∶15∶1, v/v/v) | 100 mg C18 and 200 mg magnesium sulfate | 0.1% formic acid methanol, 2 mmol/L ammonium formate aqueous solution | 0.125-1000 | 0.04-3.5, 0.125-10 | [ |
Tea | 6 | acetonitrile-water-acetic acid (79∶20∶1, v/v/v) | 150 mg C18 and 150 mg PSA | 5 mmol/L ammonium formate aqueous solution, 5 mmol/L ammonium formate methanol | - | 1, 1 | [ |
Ketchup | 5 | acetonitrile, water | 0.5 g magnesium sulfate and 100 mg C18 | 0.1% formic acid aqueous solution, acetonitrile | 0.5-200 | 1, 2.5 | [ |
Nut | 20 | acetonitrile | 0.2 g C18 | acetonitrile, 0.05% formic acid aqueous solution | 1-500 | 0.03-2.25, 0.11-7.50 | [ |
Tomato | 9 | acetonitrile-water-formic acid (84∶15∶1, v/v/v) | 200 mg C18 | 5 mmol/L ammonium acetate aqueous solution, methanol | 1-200 | 0.3-1.5, 1-10 | [ |
Fruits | 36 | acetic acid-acetonitrile- water (1∶79∶20, v/v/v) | 85 mg C18 and 15 mg PSA | 5 mmol/L ammonium acetate aqueous solution, methanol | 0.1-200 | 0.02-5, 0.1-10 | this study |
Mycotoxin | Strawberry | Grape | Pear | Peach | |||||||
---|---|---|---|---|---|---|---|---|---|---|---|
Detection rate/% | Average content/ (μg/kg) | Detection rate/% | Average content/ (μg/kg) | Detection rate/% | Average content/ (μg/kg) | Detection rate/% | Average content/ (μg/kg) | ||||
ALS | - | - | - | - | 13 | 18.65 | - | - | |||
ALT | 7 | 35.85 | - | - | - | - | - | - | |||
AME | - | - | 7 | 2.17 | - | - | 7 | 8.08 | |||
BEA | - | - | 20 | 2.04 | 7 | 2.09 | 7 | 0.19 | |||
MPA | - | - | 7 | 3.30 | - | - | - | - | |||
OTA | - | - | - | - | 7 | 0.20 | 7 | 0.13 | |||
PAT | 27 | 20.52 | 7 | 6.06 | - | - | - | - | |||
T2 | - | - | - | - | 7 | 2.58 | 7 | 0.45 | |||
TeA | - | - | - | - | 7 | 6.00 | 7 | 11.77 | |||
Ten | - | - | 13 | 0.96 | - | - | - | - | |||
ZAN | - | - | - | - | 7 | 7.00 | - | - |
表 4 实际水果样品中真菌毒素的检测结果
Table 4 Determination results of the mycotoxins in real fruit samples
Mycotoxin | Strawberry | Grape | Pear | Peach | |||||||
---|---|---|---|---|---|---|---|---|---|---|---|
Detection rate/% | Average content/ (μg/kg) | Detection rate/% | Average content/ (μg/kg) | Detection rate/% | Average content/ (μg/kg) | Detection rate/% | Average content/ (μg/kg) | ||||
ALS | - | - | - | - | 13 | 18.65 | - | - | |||
ALT | 7 | 35.85 | - | - | - | - | - | - | |||
AME | - | - | 7 | 2.17 | - | - | 7 | 8.08 | |||
BEA | - | - | 20 | 2.04 | 7 | 2.09 | 7 | 0.19 | |||
MPA | - | - | 7 | 3.30 | - | - | - | - | |||
OTA | - | - | - | - | 7 | 0.20 | 7 | 0.13 | |||
PAT | 27 | 20.52 | 7 | 6.06 | - | - | - | - | |||
T2 | - | - | - | - | 7 | 2.58 | 7 | 0.45 | |||
TeA | - | - | - | - | 7 | 6.00 | 7 | 11.77 | |||
Ten | - | - | 13 | 0.96 | - | - | - | - | |||
ZAN | - | - | - | - | 7 | 7.00 | - | - |
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