31P NMR and X-ray diffraction study of the effect of photopolymerization on lipid polymorphism

Judith A. Barry, Henry Lamparski, Michael F Brown, Fredrik Osterberg, John Cerne, Michael F. Brown, David F. O'Brien

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

It was recently shown that oligolamellar vesicles of 3:1 mixtures of dioleoylphosphatidylethanolamine (DOPE) and the photopolymerizable lipid 1,2-bis[10-(2′,4′-hexadienoyloxy)decanoyl]-sn-glycero-3- phosphocholine (SorbPC) are destabilized by polymerization of the SorbPC [Lamparski, H., Liman, U., Frankel, D. A., Barry, J. A., Ramaswami, V., Brown, M. F., & O'Brien, D. F. (1992) Biochemistry 31, 685-694]. The current work describes the polymorphic phase behavior of these mixtures in extended bilayers, as studied by 31P NMR spectroscopy and X-ray diffraction. In the NMR experiments, samples with varying degrees of polymerization were slowly raised in temperature, with spectra acquired every 2.5-10°C. In the unpolymerized mixiture, and in those photopolymerized samples where the monomeric SorbPC was decreased by 33% and 51%, an isotropic signal grew progressively until no signal from the lamellar liquid-crystalline (Lα) phase remained. In the highly polymerized sample with a 90% loss of monomeric SorbPC, less than 20% of the lipids underwent this transition. In none of the samples was an inverted hexagonal phase (HII) observed, under conditions of slow heating to almost 100°C. The X-ray diffraction studies indicated that samples which exhibit the isotropic NMR signal corresponded to a structure exhibiting no well-defined crystalline order, which upon thermal cycling became an inverted cubic phase belonging to either the Pn3m or Pn3 space groups. The temperature of the transition to the cubic precursor decreased as the extent of polymerization increased, demonstrating that photopolymerization of these lipid bilayers can significantly alter the composition and thermotropic phase behavior of the mixture.

Original languageEnglish (US)
Pages (from-to)10114-10120
Number of pages7
JournalBiochemistry
Volume31
Issue number41
StatePublished - 1992

Fingerprint

Photopolymerization
Polymorphism
X-Ray Diffraction
Nuclear magnetic resonance
Polymerization
Lipids
X ray diffraction
Phase behavior
Crystalline materials
Biochemistry
Lipid bilayers
Phosphorylcholine
Transition Temperature
Lipid Bilayers
Thermal cycling
Heating
Nuclear magnetic resonance spectroscopy
Magnetic Resonance Spectroscopy
Hot Temperature
Temperature

ASJC Scopus subject areas

  • Biochemistry

Cite this

Barry, J. A., Lamparski, H., Brown, M. F., Osterberg, F., Cerne, J., Brown, M. F., & O'Brien, D. F. (1992). 31P NMR and X-ray diffraction study of the effect of photopolymerization on lipid polymorphism. Biochemistry, 31(41), 10114-10120.

31P NMR and X-ray diffraction study of the effect of photopolymerization on lipid polymorphism. / Barry, Judith A.; Lamparski, Henry; Brown, Michael F; Osterberg, Fredrik; Cerne, John; Brown, Michael F.; O'Brien, David F.

In: Biochemistry, Vol. 31, No. 41, 1992, p. 10114-10120.

Research output: Contribution to journalArticle

Barry, JA, Lamparski, H, Brown, MF, Osterberg, F, Cerne, J, Brown, MF & O'Brien, DF 1992, '31P NMR and X-ray diffraction study of the effect of photopolymerization on lipid polymorphism', Biochemistry, vol. 31, no. 41, pp. 10114-10120.
Barry JA, Lamparski H, Brown MF, Osterberg F, Cerne J, Brown MF et al. 31P NMR and X-ray diffraction study of the effect of photopolymerization on lipid polymorphism. Biochemistry. 1992;31(41):10114-10120.
Barry, Judith A. ; Lamparski, Henry ; Brown, Michael F ; Osterberg, Fredrik ; Cerne, John ; Brown, Michael F. ; O'Brien, David F. / 31P NMR and X-ray diffraction study of the effect of photopolymerization on lipid polymorphism. In: Biochemistry. 1992 ; Vol. 31, No. 41. pp. 10114-10120.
@article{ef648938152443e1b3990ed9c66ee835,
title = "31P NMR and X-ray diffraction study of the effect of photopolymerization on lipid polymorphism",
abstract = "It was recently shown that oligolamellar vesicles of 3:1 mixtures of dioleoylphosphatidylethanolamine (DOPE) and the photopolymerizable lipid 1,2-bis[10-(2′,4′-hexadienoyloxy)decanoyl]-sn-glycero-3- phosphocholine (SorbPC) are destabilized by polymerization of the SorbPC [Lamparski, H., Liman, U., Frankel, D. A., Barry, J. A., Ramaswami, V., Brown, M. F., & O'Brien, D. F. (1992) Biochemistry 31, 685-694]. The current work describes the polymorphic phase behavior of these mixtures in extended bilayers, as studied by 31P NMR spectroscopy and X-ray diffraction. In the NMR experiments, samples with varying degrees of polymerization were slowly raised in temperature, with spectra acquired every 2.5-10°C. In the unpolymerized mixiture, and in those photopolymerized samples where the monomeric SorbPC was decreased by 33{\%} and 51{\%}, an isotropic signal grew progressively until no signal from the lamellar liquid-crystalline (Lα) phase remained. In the highly polymerized sample with a 90{\%} loss of monomeric SorbPC, less than 20{\%} of the lipids underwent this transition. In none of the samples was an inverted hexagonal phase (HII) observed, under conditions of slow heating to almost 100°C. The X-ray diffraction studies indicated that samples which exhibit the isotropic NMR signal corresponded to a structure exhibiting no well-defined crystalline order, which upon thermal cycling became an inverted cubic phase belonging to either the Pn3m or Pn3 space groups. The temperature of the transition to the cubic precursor decreased as the extent of polymerization increased, demonstrating that photopolymerization of these lipid bilayers can significantly alter the composition and thermotropic phase behavior of the mixture.",
author = "Barry, {Judith A.} and Henry Lamparski and Brown, {Michael F} and Fredrik Osterberg and John Cerne and Brown, {Michael F.} and O'Brien, {David F.}",
year = "1992",
language = "English (US)",
volume = "31",
pages = "10114--10120",
journal = "Biochemistry",
issn = "0006-2960",
publisher = "American Chemical Society",
number = "41",

}

TY - JOUR

T1 - 31P NMR and X-ray diffraction study of the effect of photopolymerization on lipid polymorphism

AU - Barry, Judith A.

AU - Lamparski, Henry

AU - Brown, Michael F

AU - Osterberg, Fredrik

AU - Cerne, John

AU - Brown, Michael F.

AU - O'Brien, David F.

PY - 1992

Y1 - 1992

N2 - It was recently shown that oligolamellar vesicles of 3:1 mixtures of dioleoylphosphatidylethanolamine (DOPE) and the photopolymerizable lipid 1,2-bis[10-(2′,4′-hexadienoyloxy)decanoyl]-sn-glycero-3- phosphocholine (SorbPC) are destabilized by polymerization of the SorbPC [Lamparski, H., Liman, U., Frankel, D. A., Barry, J. A., Ramaswami, V., Brown, M. F., & O'Brien, D. F. (1992) Biochemistry 31, 685-694]. The current work describes the polymorphic phase behavior of these mixtures in extended bilayers, as studied by 31P NMR spectroscopy and X-ray diffraction. In the NMR experiments, samples with varying degrees of polymerization were slowly raised in temperature, with spectra acquired every 2.5-10°C. In the unpolymerized mixiture, and in those photopolymerized samples where the monomeric SorbPC was decreased by 33% and 51%, an isotropic signal grew progressively until no signal from the lamellar liquid-crystalline (Lα) phase remained. In the highly polymerized sample with a 90% loss of monomeric SorbPC, less than 20% of the lipids underwent this transition. In none of the samples was an inverted hexagonal phase (HII) observed, under conditions of slow heating to almost 100°C. The X-ray diffraction studies indicated that samples which exhibit the isotropic NMR signal corresponded to a structure exhibiting no well-defined crystalline order, which upon thermal cycling became an inverted cubic phase belonging to either the Pn3m or Pn3 space groups. The temperature of the transition to the cubic precursor decreased as the extent of polymerization increased, demonstrating that photopolymerization of these lipid bilayers can significantly alter the composition and thermotropic phase behavior of the mixture.

AB - It was recently shown that oligolamellar vesicles of 3:1 mixtures of dioleoylphosphatidylethanolamine (DOPE) and the photopolymerizable lipid 1,2-bis[10-(2′,4′-hexadienoyloxy)decanoyl]-sn-glycero-3- phosphocholine (SorbPC) are destabilized by polymerization of the SorbPC [Lamparski, H., Liman, U., Frankel, D. A., Barry, J. A., Ramaswami, V., Brown, M. F., & O'Brien, D. F. (1992) Biochemistry 31, 685-694]. The current work describes the polymorphic phase behavior of these mixtures in extended bilayers, as studied by 31P NMR spectroscopy and X-ray diffraction. In the NMR experiments, samples with varying degrees of polymerization were slowly raised in temperature, with spectra acquired every 2.5-10°C. In the unpolymerized mixiture, and in those photopolymerized samples where the monomeric SorbPC was decreased by 33% and 51%, an isotropic signal grew progressively until no signal from the lamellar liquid-crystalline (Lα) phase remained. In the highly polymerized sample with a 90% loss of monomeric SorbPC, less than 20% of the lipids underwent this transition. In none of the samples was an inverted hexagonal phase (HII) observed, under conditions of slow heating to almost 100°C. The X-ray diffraction studies indicated that samples which exhibit the isotropic NMR signal corresponded to a structure exhibiting no well-defined crystalline order, which upon thermal cycling became an inverted cubic phase belonging to either the Pn3m or Pn3 space groups. The temperature of the transition to the cubic precursor decreased as the extent of polymerization increased, demonstrating that photopolymerization of these lipid bilayers can significantly alter the composition and thermotropic phase behavior of the mixture.

UR - http://www.scopus.com/inward/record.url?scp=0026611619&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0026611619&partnerID=8YFLogxK

M3 - Article

C2 - 1390768

AN - SCOPUS:0026611619

VL - 31

SP - 10114

EP - 10120

JO - Biochemistry

JF - Biochemistry

SN - 0006-2960

IS - 41

ER -