Structural Characterization of Unsaturated Phosphatidylcholines Using Traveling Wave Ion Mobility Spectrometry
- 18 September 2009
- journal article
- research article
- Published by American Chemical Society (ACS) in Analytical Chemistry
- Vol. 81 (20), 8289-8297
- https://doi.org/10.1021/ac900672a
Abstract
A number of phosphatidylcholine (PC) cations spanning a mass range of 400−1000 Da are investigated using electrospray ionization mass spectrometry coupled with traveling wave ion mobility spectrometry (TWIMS). A high correlation between mass and mobility is demonstrated with saturated phosphatidylcholine cations in N2. A significant deviation from this mass−mobility correlation line is observed for the unsaturated PC cation. We found that the double bond in the acyl chain causes a 5% reduction in drift time. The drift time is reduced at a rate of ∼1% for each additional double bond. Theoretical collision cross sections of PC cations exhibit good agreement with experimentally evaluated values. Collision cross sections are determined using the recently derived relationship between mobility and drift time in TWIMS stacked ring ion guide (SRIG) and compared to estimated collision cross sections using an empiric calibration method. Computational analysis was performed using the modified trajectory (TJ) method with nonspherical N2 molecules as the drift gas. The difference between estimated collision cross sections and theoretical collision cross sections of PC cations is related to the sensitivity of the PC cation collision cross sections to the details of the ion−neutral interactions. The origin of the observed correlation and deviation between mass and mobility of PC cations is discussed in terms of the structural rigidity of these molecules using molecular dynamic simulations.Keywords
This publication has 44 references indexed in Scilit:
- Characterizing ion mobility-mass spectrometry conformation space for the analysis of complex biological samplesAnalytical and Bioanalytical Chemistry, 2009
- Fundamentals of Traveling Wave Ion Mobility SpectrometryAnalytical Chemistry, 2008
- A study of phospholipids by ion mobility TOFMSJournal of the American Society for Mass Spectrometry, 2008
- Interactions of the Hormone Oxytocin with Divalent Metal IonsJournal of the American Chemical Society, 2008
- Gas-Phase Proton-Transfer Chemistry Coupled with TOF Mass Spectrometry and Ion Mobility-MS for the Facile Analysis of Poly(ethylene glycols) and PEGylated Polypeptide ConjugatesAnalytical Chemistry, 2008
- Monitoring copopulated conformational states during protein folding events using electrospray ionization-ion mobility spectrometry-mass spectrometryJournal of the American Society for Mass Spectrometry, 2007
- MALDI‐ion mobility‐TOFMS imaging of lipids in rat brain tissueJournal of Mass Spectrometry, 2007
- Peptides and Proteins in the Vapor PhaseAnnual Review of Physical Chemistry, 2000
- All-Atom Empirical Potential for Molecular Modeling and Dynamics Studies of ProteinsThe Journal of Physical Chemistry B, 1998
- Reduced surface: An efficient way to compute molecular surfacesBiopolymers, 1996