New view of lipid bilayer dynamics from 2H and 13C NMR relaxation time measurements

Michael F Brown, A. A. Ribeiro, G. D. Williams

Research output: Contribution to journalArticle

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Abstract

Natural abundance 13C spin-lattice (T1) relaxation time measurements are reported for unilamellar vesicles of 1,2-dipalmitoylphosphatidylcholine (1,2-dipalmitoyl-sn-glycero-3-phosphocholine), in the liquid crystalline phase, at magnetic field strengths of 1.40, 1.87, 2.35, 4.23, 7.05, 8.45, and 11.7 tesla (resonance frequencies of 15.0, 20.0, 25.1, 45.3, 75.5, 90.5, and 126 MHz, respectively), and the results are compared to previous 2H T1 studies of multilamellar dispersions. For both the 13C and 2H T1 studies, a dramatic frequency dependence of the relaxation was observed. At superconducting magnetic field strengths (4.23-11.7 tesla), plots of the 13C T1-1 relaxation rates as a function of acyl chain segment position clearly reveal the characteristic 'plateau' signature of the liquid crystalline phase, as found previously from 2H NMR studies. The dependence of T1-1 on ordering, determined previously from 2H NMR, and the T1-1 dependence on frequency, determined from both 13C and 2H NMR studies, suggest that a unified picture of the bilayer molecular dynamics can be provided by a simple relaxation law of the form T1-1 ≃ Aτf + BS2 (C-H) ω0(- 1/2 ). In the above expression, A and B are constants, S(C-H)(=S(C-D) is the bond segmental order parameter, and ω0 is the nuclear Larmor frequency. The first (A) term includes contributions from fast, local segmental motions characterized by the effective correlation time τf, whereas the second (B) term describes slower, collective fluctuations in the local ordering. The value of τf ≃ 10-11 sec, obtained by extrapolating T1-1 to infinite frequency, suggests that the segmental microviscosity of the bilayer hydrocarbon region does not differ appreciably from that of the equivalent n-paraffinic liquids of similar chain length.

Original languageEnglish (US)
Pages (from-to)4325-4329
Number of pages5
JournalProceedings of the National Academy of Sciences of the United States of America
Volume80
Issue number14 I
StatePublished - 1983
Externally publishedYes

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Lipid Bilayers
Magnetic Fields
1,2-Dipalmitoylphosphatidylcholine
Unilamellar Liposomes
Molecular Dynamics Simulation
Hydrocarbons
Carbon-13 Magnetic Resonance Spectroscopy
colfosceril palmitate

ASJC Scopus subject areas

  • General
  • Genetics

Cite this

New view of lipid bilayer dynamics from 2H and 13C NMR relaxation time measurements. / Brown, Michael F; Ribeiro, A. A.; Williams, G. D.

In: Proceedings of the National Academy of Sciences of the United States of America, Vol. 80, No. 14 I, 1983, p. 4325-4329.

Research output: Contribution to journalArticle

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title = "New view of lipid bilayer dynamics from 2H and 13C NMR relaxation time measurements",
abstract = "Natural abundance 13C spin-lattice (T1) relaxation time measurements are reported for unilamellar vesicles of 1,2-dipalmitoylphosphatidylcholine (1,2-dipalmitoyl-sn-glycero-3-phosphocholine), in the liquid crystalline phase, at magnetic field strengths of 1.40, 1.87, 2.35, 4.23, 7.05, 8.45, and 11.7 tesla (resonance frequencies of 15.0, 20.0, 25.1, 45.3, 75.5, 90.5, and 126 MHz, respectively), and the results are compared to previous 2H T1 studies of multilamellar dispersions. For both the 13C and 2H T1 studies, a dramatic frequency dependence of the relaxation was observed. At superconducting magnetic field strengths (4.23-11.7 tesla), plots of the 13C T1-1 relaxation rates as a function of acyl chain segment position clearly reveal the characteristic 'plateau' signature of the liquid crystalline phase, as found previously from 2H NMR studies. The dependence of T1-1 on ordering, determined previously from 2H NMR, and the T1-1 dependence on frequency, determined from both 13C and 2H NMR studies, suggest that a unified picture of the bilayer molecular dynamics can be provided by a simple relaxation law of the form T1-1 ≃ Aτf + BS2 (C-H) ω0(- 1/2 ). In the above expression, A and B are constants, S(C-H)(=S(C-D) is the bond segmental order parameter, and ω0 is the nuclear Larmor frequency. The first (A) term includes contributions from fast, local segmental motions characterized by the effective correlation time τf, whereas the second (B) term describes slower, collective fluctuations in the local ordering. The value of τf ≃ 10-11 sec, obtained by extrapolating T1-1 to infinite frequency, suggests that the segmental microviscosity of the bilayer hydrocarbon region does not differ appreciably from that of the equivalent n-paraffinic liquids of similar chain length.",
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N2 - Natural abundance 13C spin-lattice (T1) relaxation time measurements are reported for unilamellar vesicles of 1,2-dipalmitoylphosphatidylcholine (1,2-dipalmitoyl-sn-glycero-3-phosphocholine), in the liquid crystalline phase, at magnetic field strengths of 1.40, 1.87, 2.35, 4.23, 7.05, 8.45, and 11.7 tesla (resonance frequencies of 15.0, 20.0, 25.1, 45.3, 75.5, 90.5, and 126 MHz, respectively), and the results are compared to previous 2H T1 studies of multilamellar dispersions. For both the 13C and 2H T1 studies, a dramatic frequency dependence of the relaxation was observed. At superconducting magnetic field strengths (4.23-11.7 tesla), plots of the 13C T1-1 relaxation rates as a function of acyl chain segment position clearly reveal the characteristic 'plateau' signature of the liquid crystalline phase, as found previously from 2H NMR studies. The dependence of T1-1 on ordering, determined previously from 2H NMR, and the T1-1 dependence on frequency, determined from both 13C and 2H NMR studies, suggest that a unified picture of the bilayer molecular dynamics can be provided by a simple relaxation law of the form T1-1 ≃ Aτf + BS2 (C-H) ω0(- 1/2 ). In the above expression, A and B are constants, S(C-H)(=S(C-D) is the bond segmental order parameter, and ω0 is the nuclear Larmor frequency. The first (A) term includes contributions from fast, local segmental motions characterized by the effective correlation time τf, whereas the second (B) term describes slower, collective fluctuations in the local ordering. The value of τf ≃ 10-11 sec, obtained by extrapolating T1-1 to infinite frequency, suggests that the segmental microviscosity of the bilayer hydrocarbon region does not differ appreciably from that of the equivalent n-paraffinic liquids of similar chain length.

AB - Natural abundance 13C spin-lattice (T1) relaxation time measurements are reported for unilamellar vesicles of 1,2-dipalmitoylphosphatidylcholine (1,2-dipalmitoyl-sn-glycero-3-phosphocholine), in the liquid crystalline phase, at magnetic field strengths of 1.40, 1.87, 2.35, 4.23, 7.05, 8.45, and 11.7 tesla (resonance frequencies of 15.0, 20.0, 25.1, 45.3, 75.5, 90.5, and 126 MHz, respectively), and the results are compared to previous 2H T1 studies of multilamellar dispersions. For both the 13C and 2H T1 studies, a dramatic frequency dependence of the relaxation was observed. At superconducting magnetic field strengths (4.23-11.7 tesla), plots of the 13C T1-1 relaxation rates as a function of acyl chain segment position clearly reveal the characteristic 'plateau' signature of the liquid crystalline phase, as found previously from 2H NMR studies. The dependence of T1-1 on ordering, determined previously from 2H NMR, and the T1-1 dependence on frequency, determined from both 13C and 2H NMR studies, suggest that a unified picture of the bilayer molecular dynamics can be provided by a simple relaxation law of the form T1-1 ≃ Aτf + BS2 (C-H) ω0(- 1/2 ). In the above expression, A and B are constants, S(C-H)(=S(C-D) is the bond segmental order parameter, and ω0 is the nuclear Larmor frequency. The first (A) term includes contributions from fast, local segmental motions characterized by the effective correlation time τf, whereas the second (B) term describes slower, collective fluctuations in the local ordering. The value of τf ≃ 10-11 sec, obtained by extrapolating T1-1 to infinite frequency, suggests that the segmental microviscosity of the bilayer hydrocarbon region does not differ appreciably from that of the equivalent n-paraffinic liquids of similar chain length.

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