Chen Di, Ding Jun, Wu Ming-Ke, Zhang Tian-Yi, Qi Chu-Bo, Feng Yu-Qi
Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), Department of Chemistry, Wuhan University, Wuhan 430072, China.
Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), Department of Chemistry, Wuhan University, Wuhan 430072, China; Department of Pathology, Hubei Cancer Hospital, Wuhan 430079, China.
J Chromatogr A. 2017 Apr 14;1493:57-63. doi: 10.1016/j.chroma.2017.02.071. Epub 2017 Mar 1.
A fully automated in-tube solid phase microextraction/liquid chromatography-post column derivatization-mass spectrometry (in-tube SPME/LC-PCD-MS) method was developed for the analysis of urinary hexanal and heptanal. Online in-tube SPME enabled effective enrichment of the low level aldehydes and elimination of matrix interferences. PCD could be simply realized by mixing the LC elute and hydroxylamine hydrochloride (HAHC) solution with just a tee. The peak broadening and loss in separation efficiency associated with post column dead-volume could be ignored and even completely eliminated by employing suitable PCD configuration. What's more, HAHC is commercially available and quite cheap, and shows no contaminations to MS. The entire procedure, including the extraction of aldehydes by in-tube SPME, LC separation, post column derivatization and MS detection were integrated together and completely automated, offering competitive advantages in terms of rapidity, economy, reproducibility and simplicity. The developed protocol was then successfully performed to determine lung cancer biomarkers (hexanal, heptanal) levels in urine samples.
开发了一种全自动管内固相微萃取/液相色谱-柱后衍生化-质谱联用（管内固相微萃取/液相色谱-柱后衍生化-质谱）方法用于分析尿中的己醛和庚醛。在线管内固相微萃取能够有效富集低水平醛类并消除基质干扰。通过仅用一个三通将液相色谱洗脱液与盐酸羟胺（HAHC）溶液混合即可简单实现柱后衍生化。通过采用合适的柱后衍生化配置，与柱后死体积相关的峰展宽和分离效率损失可以忽略不计甚至完全消除。此外，HAHC有市售且相当便宜，并且对质谱无污染。整个过程，包括通过管内固相微萃取提取醛类、液相色谱分离、柱后衍生化和质谱检测，都整合在一起并完全自动化，在快速性、经济性、重现性和简便性方面具有竞争优势。然后成功地运用所开发的方法测定了尿样中肺癌生物标志物（己醛、庚醛）的水平。
