Biophysical Journal 61: 428-433 (1992)
© 1992 the Biophysical Society

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Structure of a fluid dioleoylphosphatidylcholine bilayer determined by joint refinement of x-ray and neutron diffraction data. II. Distribution and packing of terminal methyl groups.

Department of Physiology and Biophysics, University of California, Irvine 92717.

ABSTRACT

We continue in this paper the presentation of theoretical and experimental methods for the joint refinement of neutron and x-ray lamellar diffraction data for the analysis of fluid (L alpha phase) bilayer structure (Wiener, M. C., and S. H. White. 1991 a, b, c. Biophys. J. 59:162-173 and 174-185; Biochemistry. 30:6997-7008; Wiener, M. C., G. I. King, and S. H. White. Biophys. J. 60: 568-576). We show how to obtain the distribution and packing of the terminal methyls in the interior of a fluid dioleoylphosphatidylcholine bilayer (66% RH) by combining x-ray and neutron scattering-length transbilayer profiles with no a priori assumptions about the functional form of the distribution. We find that the methyls can be represented by a Gaussian function with 1/e-halfwidth of 2.95 +/- 0.28 A situated at the bilayer center. There is substantial mixing of the methyls and methylenes in the bilayer center. The Gaussian representation of the methyl distribution is narrower and has a different shape than predicted by several simulations of fluid bilayers (Gruen, D. W. R., and E. H. B. de Lacey. 1984. Surfactants in Solution, Vol. 1. Plenum Publishing Corp., New York. 279-306; de Loof, H., et al. 1991. Biochemistry. 30:2099-2133) but this may be due to the smaller area/lipid of our experiments and the presence of the double-bonds. Determination of the absolute specific volume of DOPC and an analysis of bulk alkane volumetric data over a range of hydrostatic pressures lead to estimates of methylene and methyl volumes at the bilayer center of 27 +/- 1 A3 and 57.2 +/- 3.6 A3, respectively. This result provides direct confirmation of the common assumption that the molecular packing of methyl and methylene groups in bilayers is the same as in bulk liquid alkanes.

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