Polyelectrolyte-induced domains in lipid bilayer membranes: the deuterium NMR perspective

被引:19
|
作者
Macdonald, PM [1 ]
Crowell, KJ [1 ]
Franzin, CM [1 ]
Mitrakos, P [1 ]
Semchyschyn, DJ [1 ]
机构
[1] Univ Toronto, Dept Chem, Mississauga, ON L5L 1C6, Canada
关键词
electrostatic domains; polyelectrolytes; lipid bilayers; deuterium NMR;
D O I
10.1139/bcb-76-2-3-452
中图分类号
Q5 [生物化学]; Q7 [分子生物学];
学科分类号
071010 ; 081704 ;
摘要
Domain formation in lipid bilayer membranes can occur through electrostatic interactions between charged lipids and oppositely charged polyelectrolytes, such as proteins or polynucleic acids. This review describes a novel method for examining such domains in lipid bilayers, based on H-2 NMR spectroscopy. The H-2 NMR spectrum of choline-deuterated phosphatidylcholine is sensitive to, and reports on, lipid bilayer surface charge. When a charged lipid bilayer is exposed to an oppositely charged polyelectrolyte, the latter binds electrostatically to the bilayer surface and attracts charged lipids into its vicinity. The resulting inhomogeneous charge distribution produces overlapping H-2 NMR subspectra arising from phosphatidylcholine within charge-enriched versus charge-depleted regions. Such spectral details as the quadrupolar splittings and the relative intensities of the subspectra permit a complete analysis of the domain composition, size, and, within limits, lifetime. Using H-2 NMR, domain formation in lipid bilayer membranes can be observed with both cationic and anionic polyelectrolytes, whether of natural or synthetic origin. Domain size and composition prove to be sensitive to the detailed chemical structure of both the polyelectrolyte and the charged lipids. Within the domains there is always a stoichiometric anion/cation binding ratio, indicating that the polyelectrolyte lies flat on the membrane surface. The amount of phosphatidylcholine within the domain varies as a function of its statistical availability, in accordance with the predictions of a recent thermodynamic model of domain formation. When the molecular weight of the polyelectrolyte is varied, the domain size alters in accordance with the predictions of classical polymer physics. As expected for a predominantly electrostatic phenomenon, the observed domains dissipate at high ionic strength.
引用
收藏
页码:452 / 464
页数:13
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