Poyer Salomé, Loutelier-Bourhis Corinne, Coadou Gaël, Mondeguer Florence, Enche Julien, Bossée Anne, Hess Philipp, Afonso Carlos
Normandie Université, COBRA, UMR 6014 et FR 3038, Université de Rouen, INSA de Rouen, CNRS, IRCOF,1 rue Tesnière, 76821, Mont-Saint-Aignan Cedex, France.
J Mass Spectrom. 2015 Jan;50(1):175-81. doi: 10.1002/jms.3515.
The aim of this work was to develop a reliable and efficient analytical method to characterise and differentiate saxitoxin analogues (STX), including sulphated (gonyautoxins, GTX) and non-sulphated analogues. For this purpose, hydrophilic interaction liquid chromatography (HILIC) was used to separate sulphated analogues. We also resorted to ion mobility spectrometry to differentiate the STX analogues because this technique adds a new dimension of separation based on ion gas phase conformation. Positive and negative ionisation modes were used for gonyautoxins while positive ionisation mode was used for non-sulphated analogues. Subsequently, the coupling of these three complementary techniques, HILIC-IM-MS, permitted the separation and identification of STX analogues; isomer differentiation was achieved in HILIC dimension while non-sulphated analogues were separated in the IM-MS dimension. Additional structural characteristics concerning the conformation of STXs could be obtained using IM-MS measurements. Thus, the collision cross sections (CCS) of STXs are reported for the first time in the positive ionisation mode. These experimental CCSs correlated well with the calculated CCS values using the trajectory method.
这项工作的目的是开发一种可靠且高效的分析方法，以表征和区分石房蛤毒素类似物（STX），包括硫酸化类似物（膝沟藻毒素，GTX）和非硫酸化类似物。为此，采用亲水作用液相色谱法（HILIC）分离硫酸化类似物。我们还借助离子淌度光谱法区分STX类似物，因为该技术基于离子气相构象增加了一个新的分离维度。对于膝沟藻毒素使用正离子化模式和负离子化模式，而对于非硫酸化类似物使用正离子化模式。随后，这三种互补技术HILIC-IM-MS的联用实现了STX类似物的分离和鉴定；在HILIC维度实现了异构体区分，而在IM-MS维度分离了非硫酸化类似物。使用IM-MS测量可以获得有关STX构象的其他结构特征。因此，首次报道了正离子化模式下STX的碰撞截面（CCS）。这些实验得到的CCS与使用轨迹法计算得到的CCS值相关性良好。
