Serrano María, Gallego Mercedes, Silva Manuel
Department of Analytical Chemistry, Campus of Rabanales, University of Córdoba, E-14071 Córdoba, Spain.
Department of Analytical Chemistry, Campus of Rabanales, University of Córdoba, E-14071 Córdoba, Spain.
J Chromatogr A. 2016 Mar 11;1437:241-246. doi: 10.1016/j.chroma.2016.01.056. Epub 2016 Feb 3.
Endogenous aldehydes (EAs) generated during oxidative stress and cell processes are associated with many pathogenic and toxicogenic processes. The aim of this research was to develop a solvent-free and automated analytical method for the determination of EAs in human urine using a static headspace generator sampler coupled with gas chromatography-mass spectrometry (HS-GC-MS). Twelve significant EAs used as markers of different biochemical and physiological processes, namely short- and medium-chain alkanals, α,β-unsaturated aldehydes and dicarbonyl aldehydes have been selected as target analytes. Human urine samples (no dilution is required) were derivatized with O-2,3,4,5,6-pentafluorobenzylhydroxylamine in alkaline medium (hydrogen carbonate-carbonate buffer, pH 10.3). The HS-GC-MS method developed renders an efficient tool for the sensitive and precise determination of EAs in human urine with limits of detection from 1 to 15ng/L and relative standard deviations, (RSDs) from 6.0 to 7.9%. Average recoveries by enriching urine samples ranged between 92 and 95%. Aldehydes were readily determined at 0.005-50μg/L levels in human urine from healthy subjects, smokers and diabetic adults.
氧化应激和细胞过程中产生的内源性醛类（EAs）与许多致病和产毒过程相关。本研究的目的是开发一种无溶剂的自动化分析方法，使用静态顶空发生器进样器与气相色谱-质谱联用（HS-GC-MS）测定人尿中的EAs。已选择十二种重要的EAs作为不同生化和生理过程的标志物，即短链和中链链烷醛、α,β-不饱和醛和二羰基醛作为目标分析物。人尿样品（无需稀释）在碱性介质（碳酸氢盐-碳酸盐缓冲液，pH 10.3）中用O-2,3,4,5,6-五氟苄基羟胺进行衍生化。所开发的HS-GC-MS方法为灵敏、精确地测定人尿中的EAs提供了一种有效工具，检测限为1至15 ng/L，相对标准偏差（RSD）为6.0%至7.9%。通过富集尿样，平均回收率在92%至95%之间。在健康受试者、吸烟者和糖尿病成年人的人尿中，醛类在0.005 - 50μg/L水平下易于测定。
