Commissariat à l'Energie Atomique et aux Energies Alternatives, Marcoule, Nuclear Energy Division, Radiochemistry and Processes Department , 30207 Bagnols sur Cèze.
Int J Radiat Biol. 2014 Nov;90(11):966-74. doi: 10.3109/09553002.2014.886795. Epub 2014 May 12.
The actinides are chemical poisons and radiological hazards. One challenge to better appraise their toxicity and develop countermeasures in case of exposure of living organisms is to better assess pathways of contamination. Because of the high chemical affinity of those actinide elements for phosphate groups and the ubiquity of such chemical functions in biochemistry, nucleotides and in particular adenosine triphosphate nucleotide (ATP) may be considered critical target building blocks for actinides.
Combinations of spectroscopic techniques (Fourier transformed Infra Red [FTIR], Electrospray Ionization Mass Spectrometry [ESI-MS], and Extended X-ray Absorption Fine Structure [EXAFS]) with quantum chemical calculations have been implemented in order to assess the actinides coordination arrangement with ATP.
We describe and compare herein the interaction of ATP with thorium and americium; thorium(IV) as a representative of actinide(IV) like plutonium(IV) and americium(III) as a representative of all heavier actinides. In the case of thorium, an insoluble complex is readily formed. In the case of americium, a behavior identical to that described previously for lutetium has been observed with insoluble and soluble complexes.
The comparative study of ATP complexation with Th(IV) and Am(III) shows their ability to form insoluble complexes for which a structural model has been proposed by analogy with previously described Lu(III) complexes.
锕系元素是化学毒物和放射性危害物。为了更好地评估其毒性并在生物体暴露时制定应对措施，其中一个挑战是更好地评估污染途径。由于这些锕系元素与磷酸盐基团具有很高的化学亲和力，并且在生物化学中普遍存在这种化学功能，因此核苷酸，特别是三磷酸腺苷核苷酸 (ATP)，可能被认为是锕系元素的关键靶标构建块。
采用光谱技术（傅里叶变换红外光谱 [FTIR]、电喷雾电离质谱 [ESI-MS] 和扩展 X 射线吸收精细结构 [EXAFS]）与量子化学计算相结合的方法，评估了 ATP 与锕系元素的配位排列。
我们在此描述并比较了 ATP 与钍和镅的相互作用；四价钍（IV）作为类似于四价钚（IV）的锕系元素（IV）的代表，以及三价镅（III）作为所有较重锕系元素的代表。在钍的情况下，很容易形成不溶性配合物。在镅的情况下，观察到与先前描述的镥（III）相同的行为，形成了不溶性和可溶性配合物。
对 ATP 与 Th(IV) 和 Am(III) 的配合物的比较研究表明，它们能够形成不溶性配合物，并且通过与先前描述的 Lu(III) 配合物的类比，提出了一种结构模型。
