Long-chain unsaturated fatty acids (UFA) can easily be converted on a microgram scale to the corresponding 2-a1 kenyl-4,4-dimethyloxazolines by condensation with 2-amino-2-methylpropanol (AMP). These modified molecules with a 'hidden' carboxyl group have been proved to be a class of useful derivatives for gas chromatography/mass spectrometry (GCIMS) of UFA mixtures. While possessing very good GC characteristics, the title compounds show regular, well-recognizable diagnostic ion peaks of the double bond position in the chain. Detailed description of the method as well as electron impact (El) mass spectra of derivatives resulting from mono-, di and polyenoic (maximally containing six double bonds) acids are presented.
Serum samples from kidney cancer patients and healthy controls were analyzed by both direct infusion mass spectrometry (DIMS) and liquid chromatography-mass spectrometry (LC-MS) with a high resolution ESI-Q-TOFMS. The classification and biomarker discovery capacities of the two methods were compared, and MS/MS experiments were carried out to identify potential biomarkers. DIMS had comparable classification and prediction capabilities to LC-MS but consumed only ~5% of the analysis time. With regard to biomarker discovery, twenty-three variables were found as potential biomarkers by DIMS, and 48 variables were obtained by LC-MS. DIMS is recommended to be a fast diagnostic method for kidney cancer, while LC-MS is necessary when comprehensive screening of biomarkers is required.
A compact high-irradiance laser ionization time-of-flight mass spectrometry system has been developed for the multielemental analysis of solids. Helium was introduced into the ion source as a buffer gas to cool high kinetic energy ions and suppress the interference of multicharged ions. A special pulse train repelling mode was used to achieve explicit spectra. Two quantitative methods are described for the laser ionization mass spectrometry in this paper. The first of these is the routine calibration curve quantitation, in which various matrix-matched standards are required; the second method, which is based on the uniform correlation between the signal and elemental concentration of different samples, is more convenient and covers a typical dynamic range of 6 orders. All the investigations and results indicate satisfactory performance of the newly developed instrument and its applicability for simultaneous multielemental analysis of solid samples.
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