Novel Identification of Arsenolipids Using Chemical Derivatizations in Conjunction with RP-HPLC-ICPMS/ESMS
Novel Identification of Arsenolipids Using Chemical Derivatizations in Conjunction with RP-HPLC-ICPMS/ESMS
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DOI：
10.1021/ac4020935
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发表时间：
2013-10-01
影响因子：
7.4
通讯作者：
Feldmann, Joerg
中科院分区：
文献类型：
--
作者：
Amayo, Kenneth O.;Raab, Andrea;Feldmann, Joerg
砷脂质分子结构的鉴定对于其毒理学评估和了解环境中的砷循环至关重要。然而，在脂质基质中分析这些化合物是一个持续的挑战。到目前为止，只有少数砷脂被报道，包括砷脂肪酸（AsFAs）和砷烃（AsHCs）。采用反相高效液相色谱-电感耦合等离子体质谱/电喷雾质谱联用技术对毛鳞鱼油中可能存在的新的砷脂类化合物进行了研究。在鱼油中鉴定出12种砷脂，包括3种AsFA和7种AsHC。其中，四个被确定的质子化分子量为305，331，347和359，以前没有报道过。此外，分子式为C20 H44 AsO+和C24 H44 AsO+的化合物在低浓度下被发现，并且显示出与阳离子三甲基砷基脂肪醇一致的色谱特性和MS数据。通过乙酰化和硫醇化的衍生化加上精确的质谱法被成功地用于建立这类新的砷脂作为阳离子三甲基砷基脂肪醇（TMAsFOH）的发生。
The identification of molecular structures of an arsenolipid is pivotal for its toxicological assessment and in understanding the arsenic cycling in the environment. However, the analysis of these compounds in a lipid matrix is an ongoing challenge. So far, only a few arsenolipids have been reported, including arsenic fatty acids (AsFAs) and arsenic hydrocarbons (AsHCs). By means of RP-HPLC-ICPMS/ESMS, we investigated Capelin oil (Mallotus villosus) for possible new species of arsenolipids. Twelve arsenolipids were identified in the fish oil including three AsFAs and seven AsHCs. Among the AsHCs, four that were identified had protonotated molecular masses of 305, 331, 347, and 359 and have not been reported before. In addition, the compounds with molecular formulas C20H44AsO+ and C24H44AsO+ were found in low concentrations and showed chromatographic properties and MS data consistent with cationic trimethylarsenio fatty alcohols. Derivatization by acetylation and thiolation coupled with accurate mass spectrometry was successfully used to establish the occurrence of this new class of arsenolipids as cationic trimethylarsenio fatty alcohols (TMAsFOH).