超高效液相色谱-串联质谱法同时测定水果中9种真菌毒素

利用超高效液相色谱-串联质谱法建立水果中9种真菌毒素同时检测的方法。实验对提取溶剂、净化方式及色谱质谱条件进行优化。样品经10 mmol/L柠檬酸-乙腈溶液提取，再加入氯化钠盐析，离心后上清液采用C₁₈吸附剂进行净化处理，以ACQUITY UPLC BEH C₁₈色谱柱分离，采用电喷雾正离子电离，多反应监测模式测定，以空白基质匹配标准溶液外标法定量。结果表明，9种真菌毒素在5 min内完成色谱分离分析，在各自浓度范围内呈良好线性关系（R2>0.999），方法的检出限（S/N=3）为0.004~1.676 μg/kg，定量限（S/N=10）为0.014~5.587 μg/kg。以桃、樱桃为基质，在低、中、高3个添加浓度水平下，9种真菌毒素的加标回收率在84.5%~113.2%之间，相对标准偏差为0.7%~4.0%（n=6）。将该方法用于分析实际水果样品（草莓、樱桃、葡萄、苹果、梨）中9种真菌毒素的污染状况，结果发现小粒、易腐的樱桃和葡萄中共检出白僵菌素、展青霉素、链格孢菌毒素共计7种毒素，含量在ND（未检出）~12.47 μg/kg之间。所建方法稳定、准确、灵敏、快速，能够满足水果样品中多组分真菌毒素残留分析的需求。

Simultaneous Determination of 9 Mycotoxins in Fruits by Ultra-performance Liquid Chromatography-Tandem Mass Spectrometry

An ultra-performance liquid chromatography-tandem mass spectrometry method was developed for the simultaneous determination of 9 mycotoxins in fruit. Sample extraction, purification conditions and instrument conditions were optimized. The samples were ultrasonic extracted with 10 mmol/L citric acid acetonitrile solution and salted out by adding NaCl. After centrifugation, the supernatant was cleaned up by C₁₈ sorbent and separated on an ACQUITY UPLC BEH C₁₈ column. The analytes were detected in the multiple reaction monitoring mode after being ionized by an electrospray positive ion. Quantitative analysis was performed by the external standard method using matrix-matched calibration curves. The results showed that all the 9 mycotoxins were well separated in 5 min. The coefficients of determination (R2) were greater than 0.999, suggesting good linearity of the method in the mass concentration range. The method limits of detection (3S/N) and limits of quantification (10S/N) were 0.004~1.676 μg/kg and 0.014~5.587 μg/kg, respectively. The recovery experiments were performed with peach and cherry samples at three spiked levels (low, medium and high) were 84.5%~113.2% with the relative standard deviations were 0.7%~4.0% (n=6). This method was used to analyze the contamination status of 9 mycotoxins in fruit samples (strawberry, cherry, grape, apple and pear). The results showed that beauvericin, patulin and Altenuene toxins were found in cherry and grape samples, and their contents were ranged from ND (not detected) ~12.47 μg/kg. The method is proved to be stable, accurate, sensitive and rapid, and can meet the requirements for the analysis of 9 mycotoxins residues in a variety of fruit samples.