Laboratory for Flavor Analysis and Enology, Institute of Engineering of Aragón, I3A, Department of Analytical Chemistry, Faculty of Sciences, University of Zaragoza, 50009 Zaragoza, Spain.
Anal Chim Acta. 2010 Feb 15;660(1-2):197-205. doi: 10.1016/j.aca.2009.09.041. Epub 2009 Oct 1.
This work presents a comparative study of the analytical characteristics of two methods for the analysis of carbonyl compounds in wine, both based on the derivatization with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA). In the first method derivatives are formed in the solid phase extraction (SPE) cartridge in which the analytes have been previously isolated, while in the second method derivatives are formed in a solid phase microextraction (SPME) fibre saturated with vapors of the reagent and exposed to the sample headspace. In both cases detection has been carried out by electron impact (EI) or negative chemical ionization (NCI) mass spectrometry. The possibility of determining haloanisols simultaneously has been also considered. The method based on SPE presents, in general, better analytical properties than the SPME one. Although linearity was satisfactory for both methods (R(2)>0.99), repeatability of the SPE method (RSD<10%) was better than that obtained with SPME (9% < RSD < 20%). Detection limits obtained with EI are better for the SPE method except for trihaloanisols, while with NCI detection limits for both strategies are comparable, although the SPME strategy presents worse results for ketones and methional. Detection limits are always lower with NCI, being the improvement most notable for SPME. Recovery experiments show that in the case of SPE, uncertainties are lower than 12% in all cases, while with the SPME method the imprecision plus the existence of matrix effects make the global uncertainty to be higher than 15%.
本工作对两种基于 O-(2,3,4,5,6-五氟苄基)羟胺盐酸盐（PFBHA）衍生化的葡萄酒中羰基化合物分析方法进行了比较研究。第一种方法的衍生物是在固相萃取（SPE）小柱中形成的，其中分析物已事先被分离；而第二种方法的衍生物是在充满试剂蒸气的固相微萃取（SPME）纤维中形成的，并暴露于样品顶空。在这两种情况下，检测均采用电子轰击（EI）或负离子化学电离（NCI）质谱法进行。同时还考虑了测定卤代苯甲醚的可能性。一般来说，基于 SPE 的方法比 SPME 方法具有更好的分析性能。尽管两种方法的线性度都令人满意（R(2)>0.99），但 SPE 方法的重复性（RSD<10%）优于 SPME 方法（9%<RSD<20%）。除了三卤代苯甲醚外，EI 获得的检测限更适用于 SPE 方法，而对于 NCI，两种策略的检测限相当，尽管 SPME 策略对于酮和甲硫醛的结果较差。采用 NCI 时，检测限总是较低，对于 SPME 策略而言，改进更为显著。回收实验表明，在 SPE 的情况下，在所有情况下不确定度均低于 12%，而对于 SPME 方法，不精确性加上基质效应的存在使得总不确定度高于 15%。
Zotero 插件