Instantaneous analysis of aldehydes in biological fluids using a spray interface coupled to a mass spectrometer

A new interface coupled to a mass spectrometer was developed for the direct analysis of volatile organic compounds from small volumes of aqueous samples, including blood or tissue homogenates (St-Germain et al. 1995, Anal. Chem. 67:4536-4541). The greatest advantages of our system are minimal sample treatment, an instantaneous response time coupled with detection limits in the range of < 1 ppb for most compounds. For the analysis of low-molecular weight aldehydes, such as formaldehyde, acetaldehyde, propanal, and hexanal, lower detection limits were obtained when samples were converted to methoxime derivatives prior to injection. The detection limit for hexanal in water or Krebs-Ringer solution was 0.01 microM (10 pmol injected). The reproducibility of replicate injections was 4.4%. The usefulness of our system was illustrated by measuring aldehyde accumulation in peroxidized solutions of polyunsaturated fatty acids and rat tissue homogenates. Data confirmed that peroxidation of omega-3 fatty acids produces propanal, whereas omega-6 fatty acids form hexanal. Peroxidation of heart and brain homogenates formed predominantly propanal. However, the recovery of hexanal after sample treatment with methoxylamine depended on the derivatization time and temperature, suggesting that this aldehyde may form Schiff base linkages. These results show that spray extraction coupled to mass spectrometry provides a quick (< 1 min), clean and reproducible way to detect aldehydes produced from lipid peroxidation in aqueous samples.