Zachariadis G A, Rosenberg E
Laboratory of Analytical Chemistry, Department of Chemistry, Aristotle University, University Campus, 54124 Thessaloniki, Greece.
Talanta. 2009 Apr 30;78(2):570-6. doi: 10.1016/j.talanta.2008.12.007. Epub 2008 Dec 11.
A headspace solid-phase micro-extraction (HS-SPME) method was developed and optimized for gas chromatographic separation and determination of commonly found organotin compounds in human urine after potential exposure. Butyl- and phenyltin compounds were in situ derivatized to ethylated derivatives by sodium tetraethylborate (NaBEt(4)) directly in the urine matrix. The relevant parameters affecting the yield of the SPME procedure were examined using tetrabutyltin as internal standard. The method was optimized for direct use in the analysis of undiluted human urine samples and mono-, di- and tri-substituted butyl- and phenyltin compounds could be determined after a 15-min headspace extraction time at room temperature. The selectivity of the microwave-induced plasma atomic emission detector (MIP-AED) as an element specific detector in combination with the relatively selective sample preparation technique of HS-SPME allowed the interference-free detection of the organotin compounds in all cases. A quadrupole mass spectrometer was used in parallel experiments as a detector for the confirmation of the identity molecular structure of the eluted compounds. The performance characteristics of the developed method are given for the determination of mixtures of these compounds. Finally the proposed method was applied to the analysis of several human urine samples.
建立并优化了一种顶空固相微萃取（HS-SPME）方法，用于气相色谱分离和测定潜在暴露后人体尿液中常见的有机锡化合物。在尿液基质中，通过四乙基硼酸钠（NaBEt(4)）将丁基和苯基锡化合物直接原位衍生化为乙基化衍生物。以四丁基锡为内标，考察了影响固相微萃取过程产率的相关参数。该方法经过优化，可直接用于分析未稀释的人体尿液样品，在室温下进行15分钟的顶空萃取后，可测定单、二和三取代的丁基和苯基锡化合物。微波诱导等离子体原子发射检测器（MIP-AED）作为元素特异性检测器，与相对选择性的HS-SPME样品制备技术相结合，在所有情况下都能实现有机锡化合物的无干扰检测。在平行实验中使用四极杆质谱仪作为检测器，以确认洗脱化合物的分子结构。给出了所开发方法用于测定这些化合物混合物的性能特征。最后，将所提出的方法应用于多个人体尿液样品的分析。
