Structural study of spirolide marine toxins by mass spectrometry
Structural study of spirolide marine toxins by mass spectrometry
复制标题
螺内酯海洋毒素的质谱结构研究
DOI：
10.1007/s00216-003-2297-z
复制
发表时间：
2004
影响因子：
4.3
通讯作者：
D. Volmer
中科院分区：
文献类型：
--
作者：
L. Sleno;A. Windust;D. Volmer
一组新的毒素，螺内酯，已被用几种质谱学(MS)方法研究，以使结构鉴定和代谢物鉴定成为可能。这些大环化合物由甲藻亚历山大藻产生，是一类新的海洋藻毒素，具有螺环连接的三环醚和亚胺结构。一种浮游植物粗提物已被证明含有已知的螺内酯和几种未知的化合物，存在于较低但显著的水平。本研究重点对该提取物的主要成分13-去甲基螺内酯C进行了质谱学表征，并在三四极和四极线性离子陷阱仪器上采集了碰撞诱导解离(CID)光谱。高分辨率傅里叶变换离子回旋共振MS数据揭示了质子化分子和红外多光子解离产物离子的准确质量。已经提出了这种毒素的碎裂方案来解释碰撞诱导碎片的形成。电荷远程碎裂在CID光谱中占主导地位，因为在这个分子中只有一个主要的碱性位置，并且被证明是结构信息的。广泛的13-去甲基螺内酯C的MS表征无疑将有助于表征已知和未知的螺内酯和其他相关化合物。
A novel group of toxins, the spirolides, has been investigated by several mass spectrometric (MS) methods to enable structure elucidation and metabolite identification. These macrocyclic compounds, produced by the dinoflagellate Alexandrium ostenfeldii, are a new class of marine phycotoxin with characteristic spiro-linked tricyclic ether and imine moieties. A crude phytoplankton extract has been shown to contain known spirolides and several unknown compounds, present at low yet significant levels. This study has focused on mass spectrometric characterization of the main component of this extract, 13-desmethyl spirolide C. Collision-induced dissociation (CID) spectra were collected on triple-quadrupole and quadrupole linear ion-trap instruments. High-resolution Fourier-transform ion cyclotron resonance MS data revealed the accurate masses of the protonated molecule and the product ions formed by infrared multiphoton dissociation. A fragmentation scheme for this toxin has been proposed to explain the formation of the collision-induced fragments. Charge-remote fragmentations dominate the CID spectra, because there is only one predominantly basic site in this molecule, and prove to be structurally informative. Extensive MS characterization of 13-desmethyl spirolide C will undoubtedly be useful in the characterization of known and unknown spirolides and other related compounds.