University of Copenhagen, Department of Pharmaceutics and Analytical Chemistry, Universitetsparken 2, DK-2100, Copenhagen Ø, Denmark.
Analyst. 2011 Mar 7;136(5):996-1002. doi: 10.1039/c0an00796j. Epub 2010 Dec 14.
In solution antimony exists either in the pentavalent or trivalent oxidation state. As Sb(III) is more toxic than Sb(V), it is important to be able to perform a quantitative speciation analysis of Sb's oxidation state. The most commonly applied chromatographic methods used for this redox speciation analysis do, however, often show a low chromatographic Sb recovery when samples of environmental or biological origin are analysed. In this study we explored basal chemistry of antimony and found that formation of macromolecules, presumably oligomeric and polymeric Sb(V) species, is the primary cause of low chromatographic recoveries. A combination of HPLC-ICP-MS, AFFF-ICP-MS and spin-filtration was applied for analysis of model compounds and biological samples. Quantitative chromatographic Sb redox speciation analysis was possible by acidic hydrolysis of the antimony polymers prior to analysis. Sample treatment procedures were studied and the optimum solution was acidic hydrolysis by 1 M HCl in the presence of chelating ligands (EDTA, citrate), which stabilise the trivalent oxidation state of Sb.
在溶液中，锑以五价或三价氧化态存在。由于 Sb(III) 的毒性比 Sb(V) 大，因此能够对 Sb 的氧化态进行定量形态分析非常重要。然而，用于这种氧化还原形态分析的最常用的色谱方法在分析环境或生物来源的样品时，色谱锑的回收率往往较低。在这项研究中，我们探讨了锑的基础化学，并发现形成大分子，推测是寡聚和聚合 Sb(V) 物种，是色谱回收率低的主要原因。采用 HPLC-ICP-MS、AFFF-ICP-MS 和离心过滤法分析模型化合物和生物样品。通过在分析前对锑聚合物进行酸性水解，可以进行定量的色谱锑氧化还原形态分析。研究了样品处理程序，并确定了最佳的解决方案，即在存在螯合剂（EDTA、柠檬酸盐）的情况下用 1 M HCl 进行酸性水解，这可以稳定 Sb 的三价氧化态。
