Department of Chemistry, University of Bari Aldo Moro, via Orabona 4, 70126 Bari, Italy.
Department of Chemistry, University of Bari Aldo Moro, via Orabona 4, 70126 Bari, Italy; Interdepartmental Research Center SMART, University of Bari Aldo Moro, via Orabona 4, 70126 Bari, Italy.
J Pharm Biomed Anal. 2023 Oct 25;235:115628. doi: 10.1016/j.jpba.2023.115628. Epub 2023 Aug 10.
Arsenic-containing lipids, also named arsenolipids (AsLs), are a group of organic compounds usually found in a variety of marine organisms such as fish, algae, shellfish, marine oils, and microorganisms. Numerous AsLs have been recognised so far, from simple compounds such as arsenic fatty acids (AsFAs), arsenic hydrocarbons (AsHCs), and trimethylarsenio fatty alcohols (TMAsFOHs) to more complex arsenic-containing species, of which arsenophospholipids (AsPLs) are a case in point. Mass spectrometry, both as inductively coupled plasma (ICP-MS) and liquid chromatography coupled by an electrospray source (LC-ESI-MS), was applied to organic arsenicals playing a key role in extending and refining the characterisation of arsenic-containing lipids in marine organisms. Herein, upon the introduction of a systematic notation for AsLs and a brief examination of their toxicity and biological role, the most relevant literature concerning the characterisation of AsLs in marine organisms, including edible ones, is reviewed. The use of both ICP-MS and ESI-MS coupled with reversed-phase liquid chromatography (RPLC) has brought significant advancements in the field. In the case of ESI-MS, the employment of negative polarity and tandem MS analyses has further enhanced these advancements. One notable development is the identification of the m/z 389.0 ion ([AsCHOP]) as a diagnostic product ion of AsPLs, which is obtained from the fragmentation of the deprotonated forms of AsPLs ([M - H]). The pinpointing product ions offer the possibility of determining the identity and regiochemistry of AsPL side chains. Advanced MS-based analytical methods may contribute remarkably to the understanding of the chemical diversity characterising the metalloid As in natural organic compounds of marine organisms.
含砷脂质，也称为砷脂（AsLs），是一组通常存在于各种海洋生物中的有机化合物，如鱼、藻类、贝类、海洋油和微生物。迄今为止，已经识别出许多 AsLs，从简单的化合物如砷脂肪酸（AsFAs）、砷碳氢化合物（AsHCs）和三甲基砷代脂肪醇（TMAsFOHs）到更复杂的含砷物种，其中砷磷脂（AsPLs）就是一个例子。质谱法，包括电感耦合等离子体质谱（ICP-MS）和通过电喷雾源耦合的液相色谱（LC-ESI-MS），在有机砷化合物的应用中发挥了关键作用，扩展和完善了海洋生物中含砷脂质的特征。在此，在介绍了 AsLs 的系统符号，并简要考察了它们的毒性和生物学作用之后，综述了有关海洋生物中包括可食用生物在内的 AsLs 特征描述的最相关文献。ICP-MS 和 ESI-MS 与反相液相色谱（RPLC）的结合在该领域带来了重大进展。在 ESI-MS 中，采用负极性和串联 MS 分析进一步增强了这些进展。一个值得注意的发展是鉴定出 m/z 389.0 离子（[AsCHOP]）作为 AsPLs 的诊断产物离子，该离子是从 AsPLs 的去质子形式（[M - H]）的碎裂中获得的。靶向产物离子提供了确定 AsPL 侧链的身份和区域化学的可能性。基于 MS 的先进分析方法可能对理解海洋生物中天然有机化合物中金属砷的化学多样性特征有显著贡献。
