Petit Jeremy, Geertsen Valérie, Beaucaire Catherine, Stambouli Moncef
CEA/DEN/DPC/SECR/LANIE, Bâtiment 391, 91191 Gif-sur-Yvette, France.
J Chromatogr A. 2009 May 1;1216(18):4113-20. doi: 10.1016/j.chroma.2009.02.094. Epub 2009 Mar 9.
Nuclear energy development has raised new issues like radionuclides biogeochemistry. The modelling of their biochemical properties involves the accurate determination of thermodynamical data, like stability constants. This can be achieved by using hyphenated capillary electrophoresis (CE)-ICPMS and the method was applied successfully on 1:1 lanthanum-oxalate and uranyl-oxalate complexes. Several significant steps are discussed: choice of analytical conditions, electrophoretic mobility calculation, mathematical treatment of experimental data by using linear regressions, ligand concentration and ionic strength corrections. The following values were obtained with a good precision for lanthanum-oxalate and uranyl-oxalate complexes: log(K degrees (LaOxa(+)))=6.10+/-0.10 and log(K degrees (UO(2)Oxa))=6.40+/-0.30, respectively, at infinite dilution. These values are consistent with the literature data, showing CE-ICPMS potential for metal complexes stability constants determination.
核能发展引发了诸如放射性核素生物地球化学等新问题。对其生化特性进行建模涉及到对热力学数据(如稳定常数)的精确测定。这可以通过联用毛细管电泳(CE)-电感耦合等离子体质谱(ICPMS)来实现,该方法已成功应用于1:1的镧-草酸盐和铀酰-草酸盐络合物。文中讨论了几个重要步骤:分析条件的选择、电泳迁移率的计算、使用线性回归对实验数据进行数学处理、配体浓度和离子强度校正。对于镧-草酸盐和铀酰-草酸盐络合物,在无限稀释条件下分别以良好的精度获得了以下值:log(K°(LaOxa⁺)) = 6.10 ± 0.10和log(K°(UO₂Oxa)) = 6.40 ± 0.30。这些值与文献数据一致,表明CE-ICPMS在测定金属络合物稳定常数方面具有潜力。