Disparate Molecular Dynamics of Plasmenylcholine and Phosphatidylcholine Bilayers

John H. Pak, Richard W. Gross, Vincent P. Bork, Richard E. Norberg, Michael Creer, Robert A. Wolf

Research output: Contribution to journalArticle

44 Citations (Scopus)

Abstract

The molecular dynamics of binary dispersions of plasmenylcholine/cholesterol and phospha-tidylcholine/cholesterol were quantified by electron spin resonance (ESR) and deuterium magnetic resonance ( 2 H NMR) spectroscopy. The order parameter of both 5-doxylstearate (5DS) and 16-doxylstearate (16DS) was larger in vesicles comprised of plasmenylcholine in comparison to phosphatidylcholine at all temperatures studied (e.g., = 0.592 vs. 0.487 for 5DS and 0.107 vs. 0.099 for 16DS, respectively, at 38 °C). Similarly, the order parameter of plasmenylcholine vesicles was larger than that of phosphatidylcholine vesicles utilizing either spin-labeled phosphatidylcholine or spin-labeled plasmenylcholine as probes of molecular motion. The ratio of the low-field to the midfield peak height in ESR spectra of 16-doxylstearate containing moieties (i.e., spin-labeled plasmenylcholine and phosphatidylcholine) was lower in plasmenylcholine vesicles (0.93 ± 0.01) in comparison to phosphatidylcholine vesicles (1.03 ± 0.01). 2 H NMR spectroscopy demonstrated that the order parameter of plasmenylcholine was greater than that of phosphatidylcholine for one of the two diastereotopic deuterons located at the C-2 carbon of the sn-2 fatty acyl chain. The spin-lattice relaxation times for deuteriated plasmenylcholine and phosphatidylcholine in binary mixtures containing 0–50 mol % cholesterol varied nonmonotonically as a function of cholesterol concentration and were different for each phospholipid subclass. Taken together, the results indicate that the vinyl ether linkage in the proximal portion of the sn-1 aliphatic chain of plasmenylcholine has substantial effects on the molecular dynamics of membrane bilayers both locally and at sites spatially distant from the covalent alteration.

Original languageEnglish (US)
Pages (from-to)4824-4830
Number of pages7
JournalBiochemistry
Volume26
Issue number15
DOIs
StatePublished - Jan 1 1987

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Molecular Dynamics Simulation
Phosphatidylcholines
Molecular dynamics
Cholesterol
Magnetic Resonance Spectroscopy
Deuterium
Electron Spin Resonance Spectroscopy
Nuclear magnetic resonance spectroscopy
Paramagnetic resonance
choline plasmalogens
Molecular Probes
Spin-lattice relaxation
Magnetic resonance
Binary mixtures
Dispersions
Relaxation time
Phospholipids
Carbon
Membranes
Temperature

All Science Journal Classification (ASJC) codes

  • Biochemistry

Cite this

Pak, J. H., Gross, R. W., Bork, V. P., Norberg, R. E., Creer, M., & Wolf, R. A. (1987). Disparate Molecular Dynamics of Plasmenylcholine and Phosphatidylcholine Bilayers. Biochemistry, 26(15), 4824-4830. https://doi.org/10.1021/bi00389a033
Pak, John H. ; Gross, Richard W. ; Bork, Vincent P. ; Norberg, Richard E. ; Creer, Michael ; Wolf, Robert A. / Disparate Molecular Dynamics of Plasmenylcholine and Phosphatidylcholine Bilayers. In: Biochemistry. 1987 ; Vol. 26, No. 15. pp. 4824-4830.
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abstract = "The molecular dynamics of binary dispersions of plasmenylcholine/cholesterol and phospha-tidylcholine/cholesterol were quantified by electron spin resonance (ESR) and deuterium magnetic resonance ( 2 H NMR) spectroscopy. The order parameter of both 5-doxylstearate (5DS) and 16-doxylstearate (16DS) was larger in vesicles comprised of plasmenylcholine in comparison to phosphatidylcholine at all temperatures studied (e.g., = 0.592 vs. 0.487 for 5DS and 0.107 vs. 0.099 for 16DS, respectively, at 38 °C). Similarly, the order parameter of plasmenylcholine vesicles was larger than that of phosphatidylcholine vesicles utilizing either spin-labeled phosphatidylcholine or spin-labeled plasmenylcholine as probes of molecular motion. The ratio of the low-field to the midfield peak height in ESR spectra of 16-doxylstearate containing moieties (i.e., spin-labeled plasmenylcholine and phosphatidylcholine) was lower in plasmenylcholine vesicles (0.93 ± 0.01) in comparison to phosphatidylcholine vesicles (1.03 ± 0.01). 2 H NMR spectroscopy demonstrated that the order parameter of plasmenylcholine was greater than that of phosphatidylcholine for one of the two diastereotopic deuterons located at the C-2 carbon of the sn-2 fatty acyl chain. The spin-lattice relaxation times for deuteriated plasmenylcholine and phosphatidylcholine in binary mixtures containing 0–50 mol {\%} cholesterol varied nonmonotonically as a function of cholesterol concentration and were different for each phospholipid subclass. Taken together, the results indicate that the vinyl ether linkage in the proximal portion of the sn-1 aliphatic chain of plasmenylcholine has substantial effects on the molecular dynamics of membrane bilayers both locally and at sites spatially distant from the covalent alteration.",
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Pak, JH, Gross, RW, Bork, VP, Norberg, RE, Creer, M & Wolf, RA 1987, 'Disparate Molecular Dynamics of Plasmenylcholine and Phosphatidylcholine Bilayers', Biochemistry, vol. 26, no. 15, pp. 4824-4830. https://doi.org/10.1021/bi00389a033

Disparate Molecular Dynamics of Plasmenylcholine and Phosphatidylcholine Bilayers. / Pak, John H.; Gross, Richard W.; Bork, Vincent P.; Norberg, Richard E.; Creer, Michael; Wolf, Robert A.

In: Biochemistry, Vol. 26, No. 15, 01.01.1987, p. 4824-4830.

Research output: Contribution to journalArticle

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T1 - Disparate Molecular Dynamics of Plasmenylcholine and Phosphatidylcholine Bilayers

AU - Pak, John H.

AU - Gross, Richard W.

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N2 - The molecular dynamics of binary dispersions of plasmenylcholine/cholesterol and phospha-tidylcholine/cholesterol were quantified by electron spin resonance (ESR) and deuterium magnetic resonance ( 2 H NMR) spectroscopy. The order parameter of both 5-doxylstearate (5DS) and 16-doxylstearate (16DS) was larger in vesicles comprised of plasmenylcholine in comparison to phosphatidylcholine at all temperatures studied (e.g., = 0.592 vs. 0.487 for 5DS and 0.107 vs. 0.099 for 16DS, respectively, at 38 °C). Similarly, the order parameter of plasmenylcholine vesicles was larger than that of phosphatidylcholine vesicles utilizing either spin-labeled phosphatidylcholine or spin-labeled plasmenylcholine as probes of molecular motion. The ratio of the low-field to the midfield peak height in ESR spectra of 16-doxylstearate containing moieties (i.e., spin-labeled plasmenylcholine and phosphatidylcholine) was lower in plasmenylcholine vesicles (0.93 ± 0.01) in comparison to phosphatidylcholine vesicles (1.03 ± 0.01). 2 H NMR spectroscopy demonstrated that the order parameter of plasmenylcholine was greater than that of phosphatidylcholine for one of the two diastereotopic deuterons located at the C-2 carbon of the sn-2 fatty acyl chain. The spin-lattice relaxation times for deuteriated plasmenylcholine and phosphatidylcholine in binary mixtures containing 0–50 mol % cholesterol varied nonmonotonically as a function of cholesterol concentration and were different for each phospholipid subclass. Taken together, the results indicate that the vinyl ether linkage in the proximal portion of the sn-1 aliphatic chain of plasmenylcholine has substantial effects on the molecular dynamics of membrane bilayers both locally and at sites spatially distant from the covalent alteration.

AB - The molecular dynamics of binary dispersions of plasmenylcholine/cholesterol and phospha-tidylcholine/cholesterol were quantified by electron spin resonance (ESR) and deuterium magnetic resonance ( 2 H NMR) spectroscopy. The order parameter of both 5-doxylstearate (5DS) and 16-doxylstearate (16DS) was larger in vesicles comprised of plasmenylcholine in comparison to phosphatidylcholine at all temperatures studied (e.g., = 0.592 vs. 0.487 for 5DS and 0.107 vs. 0.099 for 16DS, respectively, at 38 °C). Similarly, the order parameter of plasmenylcholine vesicles was larger than that of phosphatidylcholine vesicles utilizing either spin-labeled phosphatidylcholine or spin-labeled plasmenylcholine as probes of molecular motion. The ratio of the low-field to the midfield peak height in ESR spectra of 16-doxylstearate containing moieties (i.e., spin-labeled plasmenylcholine and phosphatidylcholine) was lower in plasmenylcholine vesicles (0.93 ± 0.01) in comparison to phosphatidylcholine vesicles (1.03 ± 0.01). 2 H NMR spectroscopy demonstrated that the order parameter of plasmenylcholine was greater than that of phosphatidylcholine for one of the two diastereotopic deuterons located at the C-2 carbon of the sn-2 fatty acyl chain. The spin-lattice relaxation times for deuteriated plasmenylcholine and phosphatidylcholine in binary mixtures containing 0–50 mol % cholesterol varied nonmonotonically as a function of cholesterol concentration and were different for each phospholipid subclass. Taken together, the results indicate that the vinyl ether linkage in the proximal portion of the sn-1 aliphatic chain of plasmenylcholine has substantial effects on the molecular dynamics of membrane bilayers both locally and at sites spatially distant from the covalent alteration.

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