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Direct Coupling of Normal-Phase High-Performance Liquid Chromatography to Atmospheric Pressure Laser Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry for the Characterization of Crude Oil
journal contribution
posted on 2013-10-15, 00:00 authored by Sami Lababidi, Saroj
K. Panda, Jan T. Andersson, Wolfgang SchraderThe
high complexity of crude oil makes the use of chromatographic
separation an important tool especially for sample simplification.
The coupling of normal-phase high-performance liquid chromatography
(HPLC) using a polar aminocyano column to a Fourier transform ion
cyclotron resonance (FTICR) mass spectrometer offers the best attributes
of good separation prior to ultrahigh resolution mass spectrometry
(MS) detection. Atmospheric pressure laser ionization (APLI) was used
as an ionization technique to analyze the nitrogen-containing aromatic
compounds in a deasphalted crude oil due to its unique selectivity
toward aromatic compounds and also due to its sensitivity. Two main
chromatographic peaks were observed during this separation indicating
a class-based separation. Mass spectra obtained from fractions were
collected along the entire retention time and compared with each other
to assign the unique constituents. By coupling the HPLC system directly
to the FTICR mass spectrometer, comparable ion and UV chromatograms
were obtained, reflecting the scan-to-scan sensitivity of the coupling
system. The results show that it is possible to calculate reconstructed
class chromatograms (RCC), allowing differences in class composition
to be traced along the retention time. As an example, radical and
protonated nitrogen species generated by APLI were detected along
the retention time which enabled a differentiation between basic and
nonbasic species in the same polar peak, thus overcoming the limitation
of chromatographic resolution. This report represents the first online
LC–FTICR MS coupling in the field of crude oil analysis.
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Atmospheric Pressure Laser Ionization Fourier Transform Ion Cyclotron Resonance Mass SpectrometryHPLCcrude oil analysiscompoundsensitivityion cyclotron resonanceAPLIseparationUVAtmospheric pressure laser ionizationMSdeasphalted crude oilFTICR mass spectrometerretention timeprotonated nitrogen speciesRCCultrahigh resolution mass spectrometryLCchromatogram
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