超高压液相色谱-高分辨质谱快速筛查和确证食用贝类中多种原多甲藻酸贝类毒素

建立超高压液相色谱-高分辨质谱快速筛查和确证贻贝、牡蛎、蚌类、扇贝等食用贝类及其制品中3 种天然形式的原多甲藻酸贝类毒素的检测方法。样品中的原多甲藻酸采用乙腈-水体系均质提取，应用改进型QuEChERS技术净化，在乙腈-水（含5 mmol/L醋酸铵和0.1%甲酸）体系经Acquity HSS T3柱（150 mm×2.1 mm，1.8 μm）梯度洗脱，实现了3 种原多甲藻酸贝类毒素的基线分离。该方法基于电喷雾正离子模式，采用高分辨质谱一级全扫描和数据依赖扫描，对食用贝类及其制品样品中的原多甲藻酸贝类毒素进行检测。3 种贝类毒素的定量限均为10 μg/kg（RSN＞10）；在10～500 μg/L范围内线性关系良好，相关系数（R2）均大于0.99。应用该方法对国内外多个地区的贝类产品进行了筛查及确证，其中部分样品检出原多甲藻酸贝类毒素。该方法灵敏度高，重复性好，操作简便、快捷，适用于食用贝类及其制品中多种原多甲藻酸贝类毒素的筛查分析。

Rapid Profiling and Confirmation of Azaspiracids in Edible Shellfishes by Ultra High Performance Liquid Chromatography-High Resolution Mass Spectrometry

An ultra high performance liquid chromatography-high resolution mass spectrometric method (UHPLC-LTQ/
Orbitrap) was developed for the rapid profiling and confirmation of 3 natural azaspiracids (AZAs) (AZA-1, AZA-2 and
AZA-3) in edible shellfishes including mussels, oysters, clams and scallops as well as related products. Samples were
homogeneously extracted with acetonitrile-water. The diluted supernatants were then purified with a modified QuEChERS
method. The separation was performed on an Acquity HSS T3 column (150 mm × 2.1 mm, 1.8 μm) by gradient elution with
acetonitrile in water containing 5 mmol/L ammonium acetate and 0.1% formic acid. The high-resolution mass spectrometry
was carried out by means of electrospray ionization in positive ion mode (ESI＋). The AZAs were detected by high-resolution
MS under full scan and data-dependent scan modes, respectively. The limits of quantification (LOQ, RSN > 10) were 10 μg/kg
for all the 3 AZA s. The calibration curves showed good linearity within the concentration range of 10 μg/L to 500 μg/L with
correlation coefficients (R2) more than 0.99. Shellfish samples from home and abroad were profiled and confirmed by the
established method. AZA s were found in some samples. Therefore this method is easy, sensitive, reproducible and efficient,
and can be applied to profile and confirm AZA s in edible shellfishes and related products.