Institute of Inorganic and Analytical Chemistry, University of Münster, Corrensstr. 48, 48149 Münster, Germany.
Institute of Plant Biochemistry and Biotechnology, University of Münster, Schlossplatz 7-8, 48143 Münster, Germany.
Sci Total Environ. 2023 Dec 20;905:166909. doi: 10.1016/j.scitotenv.2023.166909. Epub 2023 Sep 7.
Single cell-inductively coupled plasma-mass spectrometry (sc-ICP-MS) was used in this study as a valuable tool to assess the species-dependent uptake of metallopharmaceuticals into algal cells. Chlamydomonas reinhardtii algae were incubated for 24 h with four Gadolinium-based contrast agents (GBCAs) and GdCl. A species dependency towards the uptake of the tested Gd species was observed. Using single cell-ICP-MS, a Gd signal corresponding to single cell events was detected for GdCl and the linear GBCAs Omniscan® (Gadodiamide, Gd-DTPA-BMA) and Magnevist® (Gadodiamide, Gd-DTPA). For the macrocyclic complexes Dotarem® (Gadoteric acid, Gd-DOTA) and Gadovist® (Gadobutrol, Gd-BT-DO3A), no such Gd signal was visible. Total Gd analysis via ICP-MS confirmed the presence of Gd in the cells only after incubation with GdCl and the linear GBCAs, while only small amounts of Gd were detected for the incubations with macrocyclic GBCAs. Furthermore, the results showed that more Gd is bound to cell structures or macromolecules, while smaller amounts are present in the lysate. Using hydrophilic interaction liquid chromatography (HILIC)-ICP-MS, the soluble Gd species in the lysate were analyzed to determine if the initial Gd complexes were still intact. Surprisingly, no intact GBCAs were detected in the lysates of any incubation solution, possibly due to a change in Gd speciation. Further research is needed to assess which Gd species are present in the lysate, while "free" Gd ions or adducts with cell constituents are the most likely explanation. This study highlights the need for species-dependent investigation of elements in aquatic organisms. Moreover, the uptake of linear GBCAs and their species alteration raises the question of a potential accumulation of Gd in the food chain.
本研究采用单细胞感应耦合等离子体质谱法(sc-ICP-MS),作为评估金属药物在藻类细胞中摄取的物种依赖性的一种有价值的工具。将莱茵衣藻培养 24 小时,用四种钆基造影剂(GBCAs)和 GdCl 进行处理。观察到了藻类对测试的 Gd 物种摄取的物种依赖性。使用单细胞 ICP-MS,检测到 GdCl 和线性 GBCAs Omniscan®(Gadodiamide,Gd-DTPA-BMA)和 Magnevist®(Gadodiamide,Gd-DTPA)对应的单细胞事件 Gd 信号。对于大环配合物 Dotarem®(Gadoteric acid,Gd-DOTA)和 Gadovist®(Gadobutrol,Gd-BT-DO3A),则没有可见的 Gd 信号。通过 ICP-MS 进行总 Gd 分析,仅在与 GdCl 和线性 GBCAs 孵育后,才能确认细胞中存在 Gd,而对于大环 GBCAs 的孵育,则仅检测到少量 Gd。此外,结果表明,更多的 Gd 与细胞结构或大分子结合,而在裂解物中存在较少的 Gd。使用亲水相互作用液相色谱(HILIC)-ICP-MS 分析裂解物中的可溶性 Gd 物种,以确定最初的 Gd 配合物是否仍然完整。令人惊讶的是,在任何孵育溶液的裂解物中都未检测到完整的 GBCAs,这可能是由于 Gd 形态发生了变化。需要进一步研究来评估裂解物中存在哪些 Gd 物种,而“游离”Gd 离子或与细胞成分的加合物则是最有可能的解释。本研究强调了需要对水生生物中的元素进行物种依赖性研究。此外,线性 GBCAs 的摄取及其物种改变引发了关于 Gd 在食物链中潜在积累的问题。