A liquid chromatography-mass spectrometry method based on post column derivatization for automated analysis of urinary hexanal and heptanal

- A fully automated in-tube SPME/LC-PCD-MS method was developed.
- Satisfied linearity and recoveries were obtained for aldehydes analysis in urine.
- HAHC was cheap, commercially available, and showed no contaminations to MS.
- Advantages lay in rapidity, economy, reproducibility and simplicity.

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.