Dragun Zrinka, Kiralj Zoran, Fiket Željka, Ivanković Dušica
Ruđer Bošković Institute, Division for Marine and Environmental Research, Bijenička cesta 54, Zagreb, Croatia.
Environ Sci Process Impacts. 2025 Jan 22;27(1):262-276. doi: 10.1039/d4em00674g.
Technology-critical elements (TCEs) refer to the elements that play an important role in many emerging technologies and the production of advanced materials, and these include lanthanides, tungsten and vanadium. Actinides, Tl, and Pb, which also belong to TCEs, are abundantly used in power generation, industrial applications, and modern agricultural practices. The information on the influence of these elements on the aquatic environment and biota is still rather scarce. Thus, the distributions of the above-mentioned metals among cytosolic biomolecules of different molecular masses in the liver of the northern pike () from the Mrežnica River (Croatia) were studied to obtain an insight into their intracellular behaviour and potential for toxicity. The applied method was a hyphenated system of size-exclusion high-performance liquid chromatography and inductively coupled plasma mass spectrometry. In the samples with lower cytosolic concentrations, the obtained distributions of several TCEs (lanthanides, W, Th, and U) and Pb, among biomolecules of a wide range of molecular masses, which covered the entire column separation range (<10 to >600 kDa), indicated their nonspecific binding to various intracellular components. In the sample with the highest cytosolic concentration, a shift towards the highest molecular masse (>600 kDa) was observed for lanthanides and actinides, which is a sign of their possible binding to protein aggregates. In contrast, W and Pb showed a preference for medium molecular mass biomolecules (30-100 kDa). Moreover, it was hypothesized that prominent elution of U and Pb observed in the low molecular mass region (<10 kDa) possibly indicated their partial detoxification. Potential Pb associations with metallothionein-like proteins were also recorded (∼6-7 kDa). The remaining two elements, V and Tl, exhibited more specific intracellular binding, as they were eluted within one/two narrow peaks in the high molecular mass region (575 kDa/100-400 kDa). The tendency of the studied TCEs and other potentially toxic elements to bind to medium and high molecular mass intracellular proteins necessitates further research of their specific targets.
技术关键元素（TCEs）是指在许多新兴技术和先进材料生产中发挥重要作用的元素，包括镧系元素、钨和钒。同样属于TCEs的锕系元素、铊和铅，大量用于发电、工业应用和现代农业实践。关于这些元素对水生环境和生物群影响的信息仍然相当匮乏。因此，研究了克罗地亚姆雷兹尼察河的白斑狗鱼肝脏中上述金属在不同分子量的胞质生物分子中的分布情况，以深入了解它们的细胞内行为和潜在毒性。所采用的方法是尺寸排阻高效液相色谱与电感耦合等离子体质谱联用系统。在胞质浓度较低的样品中，几种TCEs（镧系元素、钨、钍和铀）以及铅在广泛分子量范围（覆盖整个柱分离范围，<10至>600 kDa）的生物分子中的分布表明它们与各种细胞内成分的非特异性结合。在胞质浓度最高的样品中，镧系元素和锕系元素向最高分子量（>600 kDa）转移，这表明它们可能与蛋白质聚集体结合。相比之下，钨和铅更倾向于中等分子量的生物分子（30 - 100 kDa）。此外，据推测，在低分子量区域（<10 kDa）观察到的铀和铅的显著洗脱可能表明它们的部分解毒作用。还记录到铅与类金属硫蛋白的潜在结合（约6 - 7 kDa）。其余两种元素钒和铊表现出更特异性的细胞内结合，因为它们在高分子量区域（575 kDa/100 - 400 kDa）的一个/两个窄峰内洗脱。所研究的TCEs和其他潜在有毒元素与中等和高分子量细胞内蛋白质结合的趋势需要对其特定靶点进行进一步研究。
