分散固相萃取-液相色谱-串联质谱法测定淡水鱼中柱孢藻毒素、节球藻毒素和微囊藻毒素

建立了同时检测淡水鱼中柱孢藻毒素、节球藻毒素、微囊藻毒素-RR、微囊藻毒素-YR及微囊藻毒素-LR的分散固相萃取-液相色谱-串联质谱方法。样品粉碎后，用乙腈-水-甲酸（89 ∶ 10 ∶ 1，v/v/v）提取目标物，C₁₈分散固相萃取柱净化，Agilent ZORBAX Eclipse XDB C₁₈色谱柱分离，乙腈和水梯度洗脱，在多反应监测（MRM）模式下进行定性分析，基质匹配标准曲线外标法定量。考察了提取溶剂及吸附剂种类对提取效率和净化效果的影响，并优化了液相色谱-串联质谱条件。该法在各自范围内具有良好线性关系，相关系数（R²）≥0.9954；检出限为5~10 μg/kg，定量限为15~40 μg/kg；样品的加标回收率为62.3%~101.2%。该方法前处理方法简单快速，灵敏高效，适用于淡水鱼中柱孢藻毒素、节球藻毒素和微囊藻毒素的有效检测。

Determination of cylindrospermopsin,nodularin and microcystins in freshwater fish by dispersive solid phase extraction-liquid chromatography-tandem mass spectrometry

A method was developed for the determination of cylindrospermopsin (CYN), nodularin (NOD), microcystin-RR (MC-RR), microcystin-YR (MC-YR) and microcystin-LR (MC-LR) in freshwater fish by dispersive solid phase extraction-liquid chromatography-tandem mass spectrometry (DSPE-LC-MS/MS). The analytes were extracted from fish tissues with acetonitrile-water-formic acid (89:10:1, v/v/v), and purified by DSPE using C₁₈ as the adsorbent. The separation of analytes was performed on an Agilent ZORBAX Eclipse XDB C₁₈ column with the gradient elution of acetonitrile and water as mobile phases. Qualitative analysis was performed using the multiple reaction monitoring (MRM) mode. The analytes were quantified by matrix-matched external standard curves. The chromatographic and MS parameters were optimized. Major factors affecting the extraction and cleanup efficiencies including the type of extraction solvent and cleanup sorbent were investigated. The linear correlation coefficients (R²) of the five target compounds were no less than 0.9954. The limits of detection (LODs, S/N=3) and limits of quantification (LOQs, S/N=10) of the five target compounds were 5-10 μg/kg and 15-40 μg/kg, respectively. The spiked recoveries of the five target compounds ranged from 62.3% to 101.2%. The developed method is simple, rapid, accurate, sensitive, and is suitable for the determination of cylindrospermopsin, nodularin and microcystins in freshwater fish.