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Differentiation and quantification of synthetic phosphatidylethanol (PEth) homologues by (1)H- and (13)C-NMR in polar organic solvents.

Wensbo Posaric, David LU ; Andersson, Anders S LU ; Bergquist, Karl-Erik and Isaksson, Anders LU (2014) In Analytical and Bioanalytical Chemistry 406(19). p.4735-4744
Abstract
Various phosphatidylethanol (PEth) derivatives, the corresponding reversed positional isomers (RPI-PEths), lyso-PEth-16:0, and penta-deuterium-labeled PEth analogs (d5-PEths), were synthesized by enzyme-independent synthetic routes. A general solvent system consisting of a mixture of acetone-d6 and methanol-d4 (97:3; v/v) was found to provide a good solubilizing capacity and excellent hydrogen-1 NMR ((1)H-NMR) peak resolution of various PEth homologues. Analytical differentiation of PEth from the corresponding RPI-PEth by carbon-13 NMR ((13)C-NMR) was demonstrated by comparison of the (13)C-NMR signals of the carbonyl groups, the allylic positions, and of the β-carbons. An exemplary stable long-term room temperature, DMSO-d6-based, and... (More)
Various phosphatidylethanol (PEth) derivatives, the corresponding reversed positional isomers (RPI-PEths), lyso-PEth-16:0, and penta-deuterium-labeled PEth analogs (d5-PEths), were synthesized by enzyme-independent synthetic routes. A general solvent system consisting of a mixture of acetone-d6 and methanol-d4 (97:3; v/v) was found to provide a good solubilizing capacity and excellent hydrogen-1 NMR ((1)H-NMR) peak resolution of various PEth homologues. Analytical differentiation of PEth from the corresponding RPI-PEth by carbon-13 NMR ((13)C-NMR) was demonstrated by comparison of the (13)C-NMR signals of the carbonyl groups, the allylic positions, and of the β-carbons. An exemplary stable long-term room temperature, DMSO-d6-based, and proton-sensitive quantitative nuclear magnetic resonance ((1)H-qNMR) independently quantified calibrator comprising PEth-16:0/18:1 for liquid chromatography (tandem) mass spectrometry (LC-MS/MS) analytical applications were prepared by employment of sodium dodecyl sulfate (SDS) as a solubilizing additive. In summary, novel hypothetically occurring PEth derivatives, e.g., RPI-PEths, have been independently synthesized with regio- and stereochemical control. Use of polar organic solvents, e.g., mixtures of acetone-d6 and methanol-d4 or DMSO-d6, improves spectral line shapes as compared to traditional hydrophobic solvents and allow for analytical differentiation between closely related PEth derivatives, as well as LC-MS/MS-independent concentration determination of dissolved single species by employment of (1)H-qNMR. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Analytical and Bioanalytical Chemistry
volume
406
issue
19
pages
4735 - 4744
publisher
Springer
external identifiers
  • pmid:24866709
  • wos:000339155500017
  • scopus:84904499295
ISSN
1618-2642
DOI
10.1007/s00216-014-7826-4
language
English
LU publication?
yes
id
a70dc689-0395-436c-8ce7-832192f96f3c (old id 4452462)
alternative location
http://www.ncbi.nlm.nih.gov/pubmed/24866709?dopt=Abstract
date added to LUP
2014-06-06 21:16:22
date last changed
2017-01-01 03:25:58
@article{a70dc689-0395-436c-8ce7-832192f96f3c,
  abstract     = {Various phosphatidylethanol (PEth) derivatives, the corresponding reversed positional isomers (RPI-PEths), lyso-PEth-16:0, and penta-deuterium-labeled PEth analogs (d5-PEths), were synthesized by enzyme-independent synthetic routes. A general solvent system consisting of a mixture of acetone-d6 and methanol-d4 (97:3; v/v) was found to provide a good solubilizing capacity and excellent hydrogen-1 NMR ((1)H-NMR) peak resolution of various PEth homologues. Analytical differentiation of PEth from the corresponding RPI-PEth by carbon-13 NMR ((13)C-NMR) was demonstrated by comparison of the (13)C-NMR signals of the carbonyl groups, the allylic positions, and of the β-carbons. An exemplary stable long-term room temperature, DMSO-d6-based, and proton-sensitive quantitative nuclear magnetic resonance ((1)H-qNMR) independently quantified calibrator comprising PEth-16:0/18:1 for liquid chromatography (tandem) mass spectrometry (LC-MS/MS) analytical applications were prepared by employment of sodium dodecyl sulfate (SDS) as a solubilizing additive. In summary, novel hypothetically occurring PEth derivatives, e.g., RPI-PEths, have been independently synthesized with regio- and stereochemical control. Use of polar organic solvents, e.g., mixtures of acetone-d6 and methanol-d4 or DMSO-d6, improves spectral line shapes as compared to traditional hydrophobic solvents and allow for analytical differentiation between closely related PEth derivatives, as well as LC-MS/MS-independent concentration determination of dissolved single species by employment of (1)H-qNMR.},
  author       = {Wensbo Posaric, David and Andersson, Anders S and Bergquist, Karl-Erik and Isaksson, Anders},
  issn         = {1618-2642},
  language     = {eng},
  number       = {19},
  pages        = {4735--4744},
  publisher    = {Springer},
  series       = {Analytical and Bioanalytical Chemistry},
  title        = {Differentiation and quantification of synthetic phosphatidylethanol (PEth) homologues by (1)H- and (13)C-NMR in polar organic solvents.},
  url          = {http://dx.doi.org/10.1007/s00216-014-7826-4},
  volume       = {406},
  year         = {2014},
}