4.8 Article

Energetic and Structural Insights into Phospholipid Transfer from Membranes with Different Curvatures by Time-Resolved Neutron Scattering

Journal

JOURNAL OF PHYSICAL CHEMISTRY LETTERS
Volume -, Issue -, Pages 6024-6030

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acs.jpclett.2c01080

Keywords

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Funding

  1. JSPS KAKENHI [17H02941, 22H02194, 20K06998, 19K16086]
  2. Terumo Life Science Foundation

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This study investigates the dynamic changes of lipids with membrane curvature, revealing that lipids in membranes with high positive curvature have unique packing properties, resulting in enhanced hydrophobic hydration and increased activation entropy. These findings provide important insights into the functions and structural changes of biomembranes.
Understanding how lipid dynamics change with membrane curvature is important given that biological membranes constantly change their curvature and morphology through membrane fusion and endo-/exocytosis. Here, we used time-resolved small-angle neutron scattering and time-resolved fluorescence to characterize the properties and dynamics of phospholipids in vesicles with different curvatures. Dissociation of phospholipids from vesicles required traversing an energy barrier comprising positive enthalpy and negative entropy. However, lipids in membranes with high positive curvature have dense acyl chain packing and loose headgroup packing, leading to hydrophobic hydration due to water penetration into the membrane. These properties were found to lower the hydrophobic hydration enhancement associated with phospholipid dissociation and mitigate the acyl chain packing of lipids adjacent to the space created by the lipid dissociation, resulting in an increase in activation entropy. The results of this study provide important insights into the functions of biomembranes in relation to their dynamic structural changes.

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