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Water order profiles on phospholipid/cholesterol membrane bilayer surfaces
Author(s) -
Robinson David,
Besley Nicholas A.,
O'shea Paul,
Hirst Jonathan D.
Publication year - 2011
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.21840
Subject(s) - membrane , hydrogen bond , chemical physics , lipid bilayer , chemistry , bilayer , molecular dynamics , molecule , dipole , crystallography , computational chemistry , organic chemistry , biochemistry
Water is pivotal in the stabilization of macromolecular biological structures, although the dynamic ensemble structure of water near to molecular surfaces has yet to be fully understood. We show, through molecular simulation and fluorescence measurements, that water at the membrane surface is substantially more ordered than bulk water, due to a loss of hydrogen bonding between water molecules, coupled with an alignment of lipid and water dipole moments. Ordering of the water leads to a gradient in the effective dielectric permittivity, which is evident in both the molecular simulations and the fluorescence measurements. A lower effective dielectric permittivity was correlated with a decreasing degree of hydrogen bonding over the same spatial range. The water molecules closest to the lipid headgroup oxygen atoms form hydrogen bonds which exhibit a mean lifetime of 6.3 ps, compared with a mean lifetime of water‐water hydrogen bonds of less than 2 ps. Membranes made up purely of phosphatidylcholine (PC) were compared with those made with a PC/cholesterol ratio relevant to cell membranes. Clear differences were found between these membrane configurations. These observations point to molecular structural differences in the surface environments of membranes and may underlie regional differences in the surface biophysical properties of membrane microdomains. © 2011 Wiley Periodicals, Inc. J Comput Chem, 2011.