Zachariadis G A, Rosenberg E
Institute of Chem. Technologies and Analytics, Vienna University of Technology, 1060 Vienna, Austria.
J Chromatogr B Analyt Technol Biomed Life Sci. 2009 Apr 15;877(11-12):1140-4. doi: 10.1016/j.jchromb.2009.02.065. Epub 2009 Mar 5.
A method for the determination of organotin compounds in urine samples based on liquid-liquid extraction (LLE) in hexane and gas chromatographic separation was developed and optimized. Seven organotin species, namely monobutyltin (MBT), dibutyltin (DBT), tributyltin (TBT), tetrabutyltin (TeBT), monophenyltin (MPhT), diphenyltin (DPhT) and triphenyltin (TPhT), were in situ derivatized by sodium tetraethylborate (NaBEt(4)) to form ethylated less polar derivatives directly in the urine matrix. The critical parameters which have a significant effect on the yield of the successive liquid-liquid extraction procedure were examined, by using standard solutions of tetrabutyltin in hexane. The method was optimized for use in direct analysis of undiluted human urine samples and ways to overcome practical problems such as foam formation during extraction, due to various constituents of urine are discussed. After thorough optimization of the extraction procedure, all examined species could be determined after 3 min of simultaneous derivatization and extraction at room temperature and 5 min phase separation by centrifugation. Gas chromatography with a microwave-induced plasma atomic emission detector (MIP-AED) as element specific detector was employed for quantitative measurements, while a quadrupole mass spectrometric detector (MS) was used as molecular specific detector. The detection limits were between 0.42 and 0.67 microg L(-1) (as Sn) for the quantitative LLE-GC-MIP-AED method and the precision between 4.2% and 11.7%, respectively.
建立并优化了一种基于己烷液液萃取（LLE）和气相色谱分离测定尿样中有机锡化合物的方法。七种有机锡化合物，即一丁基锡（MBT）、二丁基锡（DBT）、三丁基锡（TBT）、四丁基锡（TeBT）、一苯基锡（MPhT）、二苯基锡（DPhT）和三苯基锡（TPhT），通过四乙基硼酸钠（NaBEt(4)）原位衍生，直接在尿液基质中形成极性较小的乙基化衍生物。使用己烷中的四丁基锡标准溶液，研究了对连续液液萃取过程产率有显著影响的关键参数。该方法针对未稀释的人类尿液样本的直接分析进行了优化，并讨论了克服实际问题（如由于尿液中的各种成分导致萃取过程中形成泡沫）的方法。在对萃取程序进行全面优化后，所有检测的化合物在室温下同时衍生和萃取3分钟，然后通过离心进行5分钟相分离后即可测定。采用带有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的气相色谱进行定量测量，同时使用四极杆质谱检测器（MS）作为分子特异性检测器。定量LLE-GC-MIP-AED方法的检测限在0.42至0.67 μg L(-1)（以Sn计）之间，精密度分别在4.2%至11.7%之间。
