Membrane water-penetration profiles from spin labels

@article{Marsh2002MembraneWP,
  title={Membrane water-penetration profiles from spin labels},
  author={D. Marsh},
  journal={European Biophysics Journal},
  year={2002},
  volume={31},
  pages={559-562}
}
  • D. Marsh
  • Published 2002
  • Chemistry, Medicine
  • European Biophysics Journal
Abstract. Spin label hyperfine splittings in mixtures of protic and aprotic solvents are used to obtain association constants KA,h for hydrogen bonding to oxazolidine nitroxides. With the Onsager approach to account for the variation in local dielectric constant, these results are used to determine the effective penetration profile of water into fluid phospholipid membranes, from recent electron paramagnetic resonance (EPR) studies on phospholipids spin-labelled systematically down the sn-2… Expand
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67 Citations
Background Citations
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Methods Citations
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Results Citations
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67 Citations

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Citation Type

Spin-Label EPR for Determining Polarity and Proticity in Biomolecular Assemblies: Transmembrane Profiles
  • D. Marsh
  • Chemistry, Medicine
  • Applied magnetic resonance
  • 2010
TLDR
Applications to studies of the transverse polarity profiles in lipid bilayers, which constitute the permeability barrier of biological membranes, are reviewed and emphasis is given to parallels with the permeation profiles of oxygen and nitric oxide that are determined by using nonlinear continuous-wave EPR and saturation recovery EPR. Expand
Oxygen permeation profile in lipid membranes: comparison with transmembrane polarity profile.
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TLDR
The association of water (D(2)O) with phospholipid membranes was studied by using pulsed-electron spin resonance techniques and results are in good agreement with more indirect measurements of the transmembrane polarity profile that are based on the (14)N-hyperfine splittings in the conventional continuous-wave electron spin resonance spectrum. Expand
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Nitroxide spin-labelled lipid analogues are often used to study model membrane properties using EPR spectroscopy. Whereas in liquid phase membranes the spin label assumes, on average, its putative… Expand
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Electron spin-echo envelope modulation (ESEEM) spectroscopy was used to investigate the water exposure of TOAC-alamethicin introduced into membranes of saturated or unsaturated diacyl phosphatidylcholines that were dispersed in D2O, consistent with proposals of a critical concentration for switching between the two different membrane-associated states. Expand
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The ESR parameters of PC spin labels in frozen membranes do not simply represent the membrane polarity or water penetration profile. Instead, they show a distribution between hydrogen-bonded (HB) and… Expand
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The correlation between datasets for TOAC and DOXYL nitroxides in the various solvents is used to establish the polarity profile for isotropic hyperfine couplings of TOAC in a transmembrane peptide. Expand
Librational motion of spin-labeled lipids in high-cholesterol containing membranes from echo-detected EPR spectra.
TLDR
Two-pulse, echo-detected electron paramagnetic resonance (EPR) spectroscopy was used to study the librational motions of spin-labeled lipids in membranes of dipalmitoylphosphatidylcholine + 50 mol % cholesterol, which are important for glass-like states and are generally relevant to high lipid packing densities, e.g., in cholesterol-containing raft domains and condensed complexes. Expand
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References

SHOWING 1-7 OF 7 REFERENCES
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  • D. Marsh
  • Chemistry, Medicine
  • Journal of magnetic resonance
  • 2002
A self-consistent treatment of reaction field effects on isotropic (14)N hyperfine coupling constants of nitroxide spin labels in mixtures of polar and apolar solvents is given based on the Onsager… Expand
Medium effects on ESR spectra in studies of hydrogen-bonded transient solvent-solute complexes
The effect of solvent polarity on the observed hyperfine coupling constants of nitroxide radicals has been investigated both in the presence of and in the absence of hydrogen donors. With inert… Expand
Hydrogen bond contribution to the isotropic hyperfine splitting constant of a nitroxide free radical
Abstract The increase in hyperfine splitting constant of nitroxide, due to hydrogen bond formation between the NO group of the radical and the solvent molecule is shown to be proportional to the… Expand
Polarity and permeation profiles in lipid membranes
  • D. Marsh
  • Chemistry, Medicine
  • Proceedings of the National Academy of Sciences of the United States of America
  • 2001
TLDR
The results are relevant not only to the permeation of water and polar solutes into membranes and their permeabilities, but also to depth determinations of site-specifically spin-labeled protein residues by using paramagnetic relaxation agents. Expand
SOLUBILITIES OF WATER IN SEVERAL NORMAL ALKANES FROM C7 TO C161
THE SOLVENT EFFECT ON DI-TERT-BUTYL NITROXIDE. A DIPOLE-DIPOLE MODEL FOR POLAR SOLUTES IN POLAR SOLVENTS
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