International audienceThe present work describes the first differentiation of enantiomers using the coupling of traveling wave ion mobility and mass spectrometry (TWIM-MS). This study was carried out on amino acids, the building blocks of proteins, which together with nucleotides, polysaccharides or lipids, are the main constituents of all living organisms. Herein, the enantiomers of aromatic amino acids (AA) such as phenylalanine, tryptophan and tyrosine are differentiated by TWIM-MS through their cationisation with copper(II) and multimer formation with D-proline (Pro) as a chiral reference compound. This methodology can be considered as an alternative approach to conventional methods for the separation of enantiomers. Moreover, quantification of the enantiomers can be performed easily and quickly using TWIM-MS analysis of the ionic complex [((D)Pro)(2)+(D/L)AA+Cu-II-H](+)
Petroprophyrins are
biomarkers used to extract information about
petroleum genesis among other characteristics. Identification of particular
types, such as Ni, Cu, Mn, vanadyl (VO), and oxygenated or sulfur-containing
porphyrins, typically involves exhaustive isolation and purification
processes followed by high-resolution mass spectrometry analysis using
atmospheric pressure photoionization [APPI-(+)] or electrospray [ESI-(+)]
sources. Simultaneous identification of all porphyrins present in
a particular crude oil or organic-matter-rich sediment still remains
an analytical challenge. Here, we report a straightforward petroporphyrin
isolation and identification methodology based on a single-step liquid–liquid
(L–L) extraction (crude oil: acetonitrile) and high-performance
thin-layer chromatography fractionation (HPTLC, aminopropyl-bonded
silica) followed by selective ionization via electron transfer in
matrix-assisted laser desorption ionization (MALDI-FTICR). Mass spectrometric
analysis of the extracts resulted in detection of 350 individual compounds
in the acetonitrile extract and 518 in the HPTLC extract, corresponding
to the porphyrin families N4VO, N4VO2, N4VO3, N4VOS, and N4Ni as verified by isotopic structure analysis. To the best of our
knowledge, this observation constitutes the largest simultaneous identification
of Ni, VO, and oxygenated and sulfur-containing porphyrins in a single
crude oil sample. In addition, the use of MALDI significantly reduces
the amount of sample required for analysis (pico to femtomole levels)
in comparison with continuous infusion methods such as APPI and ESI.
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