Universidad Autónoma de Puebla, Centro de Química ICUAP, Apdo, Postal J-55 Puebla, Puebla 72571, Mexico.
Talanta. 2010 Jun 30;82(1):38-43. doi: 10.1016/j.talanta.2010.03.054. Epub 2010 Apr 2.
Arsenic is a metalloid well known to be potentially toxic depending of its species. Lipid-soluble arsenicals (arsenolipids) are present in a wide range of biological samples in which they could play a role in the biosynthesis of organoarsenic compounds from inorganic arsenic compounds. Arsenolipids have recently attracted considerable interest. In order to gain deeper insights into the impact of arsenolipids new analytical approaches for reliable determination of this class of arsenic-containing hydrocarbons in various matrices are needed. High concentrations of arsenolipids were found in seafood which served as sample material in this study. We report the investigation of three arsenolipids found in canned cod liver from which they were extracted and purified by solid phase extraction (SPE) using a silica gel column and ethyl acetate/methanol as eluent. Analytical studies were conducted by means of gas chromatography coupled with ICP-MS, MIP-AES and EI-qMS and by TOF-MS. The results obtained by GC-ICP-MS and GC-MIP-AES showed the existence of numerous arsenic compounds in the SPE fractions collected. Three major peaks were found within a retention time window between 10 and 25 min. The presence of arsenic compounds in the fish tissue could be confirmed using GC-EI-qMS analysis. Corresponding information of the molecular weights of the major arsenic species were provided by TOF-MS which allows highly accurate mass determinations. The results showed the presence of the arsenic-containing hydrocarbons with the following molecular formulas: C(17)H(37)AsO (calculated for M+H 333.2133; found 333.2136; Deltam=0.90 ppm); C(19)H(41)AsO (calculated for M+H 361.2446; found 361.2446; Deltam=0.00 ppm); C(23)H(37)AsO (calculated for M+H 405.2133; found 405.2145; Deltam=2.96 ppm). Suggestions for the corresponding structures are discussed.
砷是一种众所周知的潜在有毒金属元素,其毒性取决于其种类。脂溶性砷化合物(砷脂)存在于广泛的生物样本中,它们可能在无机砷化合物向有机砷化合物的生物合成中发挥作用。砷脂最近引起了相当大的关注。为了更深入地了解砷脂的影响,需要开发新的分析方法来可靠地测定各种基质中这类含砷碳氢化合物。在本研究中,高浓度的砷脂存在于海鲜中,这些海鲜被用作样本材料。我们报告了在罐装鳕鱼肝中发现的三种砷脂的研究,这些砷脂是通过固相萃取(SPE)用硅胶柱和乙酸乙酯/甲醇作为洗脱液提取和纯化的。分析研究通过气相色谱与电感耦合等离子体质谱(GC-ICP-MS)、微波诱导等离子体原子发射光谱(MIP-AES)和电子轰击-质谱(EI-qMS)以及飞行时间质谱(TOF-MS)进行。GC-ICP-MS 和 GC-MIP-AES 的结果表明,在收集的 SPE 馏分中存在许多砷化合物。在 10 到 25 分钟的保留时间窗口内发现了三个主要峰。GC-EI-qMS 分析证实了鱼组织中砷化合物的存在。TOF-MS 提供了主要砷物种的分子量的相应信息,允许进行高度准确的质量测定。结果表明,存在以下分子式的含砷碳氢化合物:C(17)H(37)AsO(计算M+H为 333.2133;实测值为 333.2136;差值为 0.90 ppm);C(19)H(41)AsO(计算M+H为 361.2446;实测值为 361.2446;差值为 0.00 ppm);C(23)H(37)AsO(计算M+H为 405.2133;实测值为 405.2145;差值为 2.96 ppm)。讨论了相应结构的建议。