Valeri Anna Lucia, Kremser Leopold, Raggi Maria Augusta, Grüner Bohumir, Vespalec Radim, Kenndler Ernst
Institute of Analytical Chemistry, University of Vienna, Vienna, Austria.
Electrophoresis. 2008 Apr;29(8):1658-66. doi: 10.1002/elps.200700815.
The electrophoretic properties of boron cluster compounds were determined in water, methanol and ACN as solvents of the BGE and discussed based on the principles of ion migration. Two types of boron cluster compounds were investigated. One type consisted of derivatives of the nido-7,8-dicarbaundecaborate cluster, the other types are derivatized cobalt bis(dicarbollide) ions (COSANs) whose central cobalt atom is sandwiched by two 7,8-dicarbaundecaborate clusters. The BGE in all solvents was acetate/acetic acid buffer with pH 4.75 in water, 9.7 in methanol and 22.3 in ACN, respectively, at different ionic strength between 5 and 30 mM. The dependence of the mobility on ionic strength could not be explained by the theory of Debye, Hückel and Onsager, but good agreement was found upon considering an ion size parameter. Limiting mobilities were derived by curve fitting, and by the aid of the solvent viscosities the hydrodynamic radii of the analyte anions were calculated. They are between 0.25 and 0.48 nm, and were nearly independent of the solvent. Electrophoresis of the analytes in a BGE consisting of 6 mM perchloric acid in ACN allows the conclusion that the present boron cluster compounds behave as stronger acids than perchloric acid.
在水、甲醇和乙腈作为背景电解质(BGE)溶剂的条件下测定了硼簇化合物的电泳性质,并基于离子迁移原理进行了讨论。研究了两种类型的硼簇化合物。一种类型由巢式-7,8-二碳代十一硼烷簇的衍生物组成,另一种类型是中心钴原子被两个7,8-二碳代十一硼烷簇夹在中间的衍生化双(二碳硼烷)钴离子(COSANs)。在所有溶剂中,BGE分别为醋酸盐/醋酸缓冲液,在水中pH为4.75,在甲醇中pH为9.7,在乙腈中pH为22.3,离子强度在5至30 mM之间。迁移率对离子强度的依赖性无法用德拜、休克尔和昂萨格理论来解释,但在考虑离子尺寸参数时发现了良好的一致性。通过曲线拟合得出极限迁移率,并借助溶剂粘度计算分析物阴离子的流体动力学半径。它们在0.25至0.48 nm之间,且几乎与溶剂无关。在由乙腈中6 mM高氯酸组成的BGE中对分析物进行电泳,可以得出结论:目前的硼簇化合物表现出比高氯酸更强的酸性。