The presence of 12β-deoxydecarbamoylsaxitoxin in the Japanese toxic dinoflagellate Alexandrium determined by simultaneous analysis for paralytic shellfish toxins using HILIC-LC-MS/MS
The presence of 12β-deoxydecarbamoylsaxitoxin in the Japanese toxic dinoflagellate Alexandrium determined by simultaneous analysis for paralytic shellfish toxins using HILIC-LC-MS/MS
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DOI：
10.1016/j.hal.2015.09.003
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发表时间：
2015-11-01
期刊：
影响因子：
6.6
通讯作者：
Yotsu-Yamashita, Mari
中科院分区：
文献类型：
--
作者：
Cho, Yuko;Tsuchiya, Shigeki;Yotsu-Yamashita, Mari
采用高分辨率（HR）-亲水相互作用色谱（HILIC）-电喷雾电离（ESI）-四极杆飞行时间质谱（Q-TOF MS）对海洋甲藻有毒亚克隆Alexandiumtamarense Axat-2和来自同一日本分离株的无毒亚克隆UAT-014-009中的石房蛤毒素（SIX）类似物进行了鉴别筛选研究。一种未知化合物仅在毒性亚克隆中被鉴定，并被发现具有分子式C9 H16 N6 O2。这种结构与十氨甲酰基STX（dcSTX; C9 H16 N6 O3）的结构不同之处在于失去了一个氧。12-脱氧-dcSTX标准品（12 α-和β-脱氧-dcSTX的混合物）通过用硼氢化钠还原由dcSTX化学制备。在A.通过比较其HR-HILIC-LC-MS保留时间和HR-MS/MS光谱与化学制备的标准品的保留时间和HR-MS/MS光谱，将tamarense鉴别为12 β-脱氧-dcSTX，并通过柱后荧光衍生化的高灵敏度HPLC分析确认鉴别。此外，还对A. catenella的毒素谱与A.还发现tamarense含有12 β-脱氧-dcSTX。以前，12 β-脱氧-dcSTX是从淡水蓝藻Lyngbya wollei中分离出来的，它产生一组独特的SIX类似物。这项研究是海洋甲藻中存在12 β-脱氧-dcSTX的第一个证据。(C)2015 Elsevier B. V.版权所有。
A differential screening study using high-resolution (HR)-hydrophilic interaction chromatography (HILIC)-electrospray ionization (ESI)-quadrupole time-of-flight mass spectrometry (Q-TOF MS) was conducted to identify saxitoxin (SIX) analogues in the marine dinoflagellate toxic sub-clone Alexandrium tamarense Axat-2 and the non-toxic sub-clone UAT-014-009 derived from the same Japanese isolate. One unknown compound was identified only in the toxic sub-clone and was found to have the molecular formula C9H16N6O2. This structure differed from that of decarbamoyl STX (dcSTX; C9H16N6O3) by the loss of a single oxygen. A 12-deoxy-dcSTX standard (a mixture of 12 alpha- and beta-deoxy-dcSTX) was chemically prepared from dcSTX by reduction with sodium borohydride. The unknown compound in the toxic strain of A. tamarense was identified as 12 beta-deoxy-dcSTX by comparison of its HR-HILIC-LC-MS retention time and HR-MS/MS spectrum with those of the chemically prepared standard, and the identification was confirmed by high-sensitivity HPLC analysis with post-column fluorescent derivatization. Moreover, two Japanese isolates of A. catenella showing toxin profiles different from that of A. tamarense were also found to contain 12 beta-deoxy-dcSTX. Previously, 12 beta-deoxy-dcSTX was isolated from the freshwater cyanobacterium Lyngbya wollei, which produces a unique set of SIX analogues. This study is the first evidence of the presence of 12 beta-deoxy-dcSTX in marine dinoflagellates. (C) 2015 Elsevier B.V. All rights reserved.