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Acyl chain conformational ordering in liquid-crystalline bilayers: comparative FT-IR and 2H-NMR studies of phospholipids differing in headgroup structure and chain length

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Abstract

FT-IR spectroscopy has been used to evaluate the acyl chain conformational ordering of DMPC, DMPE, DMPA (pH 6 and 12), DMPG (pH 1 and 7), and DPPC, DPPE, DPPA (pH 6). The frequencies of the symmetric and antisymmetric methylene stretching vibrations were determined as a function of temperature. In the liquid-crystalline phase the frequencies show a qualitative dependence on the amount of chain disorder. Quantitative data for trans-gauche isomerization were obtained from the integral intensities of the conformation sensitive methylene wagging absorptions at ca. 1368 cm−1 (gtg′ and gtg sequences), 1356 cm −1 (double gauche) and 1342 cm−1 (end gauche). The integral band intensities were converted to the number of gauche conformers per acyl chain using the calibration factors published by Senak et al. (1991). At 69°C the highest number of gauche conformers excluding contributions from single gauche conformers and jogs (g′tttg) are found for PCs (DMPC: 2.6; DPPC: 2.4), followed by DMPG− (2.0), phosphatidylethanolamines (DMPE: 1.4; DPPE: 2.0), protonated DMPG (1.5), and phosphatidic acids (DPPA−: 1.7; DMPA−: 1.4, DMPA2−: 1.7). From 2H-NMR measurements of perdeuterated samples of DMPC, DMPA, DPPC, and DPPA the quadrupolar splittings Δν Q⊥i and the order parameter S CDi of the CD2-segments close to the chain ends could be determined whereas splittings in the plateau region of the chains could not be resolved. The quadrupolar splittings are affected by trans-gauche isomerization, long axis rotation, and restricted wobbling motions of the acyl chains. In the simplest assumption, the order parameter SCD can be expressed as a product of a segmental order parameter Sγ and a lhain order parameter S α. For comparison of the different lipids we used average order parameters SCD, obtained by averaging over all \(S_{CDi^ - }\) values, and Sγ determined from the total number of gauche conformers per chain by FT-IR-spectroscopy, to calculate an empirical average chain order parameter Sα. The combination of 2H-NMR and FT-IR results allows the estimation of the relative extent of chain wobbling for the different lipid molecules. Sα is lowest for PCs (Sα ≈ 0.475) while PEs (Sα≈ 0.51) and PAs (Sα≈0.52) show less chain wobbling.

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Abbreviations

FT-IR:

Fourier transform infrared

2H-NMR:

deuterium nuclear magnetic resonance

DMPC(−d54):

(perdeuterated) dimyristoyl-phosphatidylcholine

DMPE(−d54):

(perdeuterated) dimyristoyl-phosphatidylethanolamine

DMPA(−d54):

(perdeuterated) dimyristoyl-phosphatidic acid

DMPG:

dimyristoyl-phosphatidylglycerol

DPPC(−d62):

(perdeuterated) dipalmitoyl-phosphatidylcholine

DPPE(−d62):

(perdeuterated) dipalmitoyl-phosphatidylethanolamine

DPPA(−d62):

(perdeuterated) dipalmitoyl-phosphatidic acid

gtg:

gauche ±-trans-gauche±

gtg′:

gauche±-trans-gauche±

dg:

double gauche

eg:

end gauche

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Authors and Affiliations

  1. Fachbereich Chemie der Universität Kaiserslautern, Postfach 30 49, D-67653, Kaiserslautern, Germany

    Jürgen Tuchtenhagen, Wolfgang Ziegler & Alfred Blume

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  1. Jürgen Tuchtenhagen
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  2. Wolfgang Ziegler
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  3. Alfred Blume
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Correspondence to: A. Blume

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Tuchtenhagen, J., Ziegler, W. & Blume, A. Acyl chain conformational ordering in liquid-crystalline bilayers: comparative FT-IR and 2H-NMR studies of phospholipids differing in headgroup structure and chain length. Eur Biophys J 23, 323–335 (1994). https://doi.org/10.1007/BF00188656

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  • DOI: https://doi.org/10.1007/BF00188656

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