| A comparison of the gas phase acidities of phospholipid headgroups: experimental and computational studies. | |
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MedLine Citation:
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PMID: 15907707 Owner: NLM Status: MEDLINE |
Abstract/OtherAbstract:
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Proton-bound dimers consisting of two glycerophospholipids with different headgroups were prepared using negative ion electrospray ionization and dissociated in a triple quadrupole mass spectrometer. Analysis of the tandem mass spectra of the dimers using the kinetic method provides, for the first time, an order of acidity for the phospholipid classes in the gas phase of PE < PA << PG < PS < PI. Hybrid density functional calculations on model phospholipids were used to predict the absolute deprotonation enthalpies of the phospholipid classes from isodesmic proton transfer reactions with phosphoric acid. The computational data largely support the experimental acidity trend, with the exception of the relative acidity ranking of the two most acidic phospholipid species. Possible causes of the discrepancy between experiment and theory are discussed and the experimental trend is recommended. The sequence of gas phase acidities for the phospholipid headgroups is found to (1) have little correlation with the relative ionization efficiencies of the phospholipid classes observed in the negative ion electrospray process, and (2) correlate well with fragmentation trends observed upon collisional activation of phospholipid [M - H](-) anions. |
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Authors:
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Michael C Thomas; Todd W Mitchell; Stephen J Blanksby |
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Publication Detail:
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Type: Comparative Study; Journal Article; Research Support, Non-U.S. Gov't Date: 2005-04-26 |
Journal Detail:
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Title: Journal of the American Society for Mass Spectrometry Volume: 16 ISSN: 1044-0305 ISO Abbreviation: J. Am. Soc. Mass Spectrom. Publication Date: 2005 Jun |
Date Detail:
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Created Date: 2005-05-23 Completed Date: 2006-03-17 Revised Date: 2006-11-15 |
Medline Journal Info:
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Nlm Unique ID: 9010412 Medline TA: J Am Soc Mass Spectrom Country: United States |
Other Details:
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Languages: eng Pagination: 926-39 Citation Subset: IM |
Affiliation:
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Department of Chemistry, University of Wollongong, Northfields Road, Wollongong, New South Wales 2522, Australia. |
Export Citation:
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APA/MLA Format Download EndNote Download BibTex |
| MeSH Terms | |
Descriptor/Qualifier:
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Acids
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chemistry Computational Biology Electrochemistry Gases / chemistry* Hydrogen-Ion Concentration Kinetics Mass Spectrometry Models, Molecular Molecular Structure Phospholipids / chemistry* |
| Chemical | |
Reg. No./Substance:
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0/Acids; 0/Gases; 0/Phospholipids |
From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine
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