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Optical and molecular features of negatively curved surfaces created by POPE lipids: A crucial role of the initial conditions. | LitMetric

Optical and molecular features of negatively curved surfaces created by POPE lipids: A crucial role of the initial conditions.

Spectrochim Acta A Mol Biomol Spectrosc

Division of Organic Chemistry and Biochemistry, Ruđer Bošković Institute, Bijenička 54, 10000 Zagreb, Croatia. Electronic address:

Published: September 2024

Membrane fusion is closely related to plasma membrane domains rich in cone-shaped phosphatidylethanolamine (PE) lipids that can reverse membrane curvature under certain conditions. The phase transition of PE-based lipid membranes from the lamellar fluid phase (L) to the inverse hexagonal phase (H) is commonly taken as a general model in reconstructing the membrane fusion pathway, and whose structural features have been mostly described so far using structural and microscopic techniques. The aim of this paper is to decipher the optical and molecular features of L → L and especially of L → H transition of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoethanolamine (POPE) lipids at pH = 7.0 when they are initially prepared in the form of both multi- and unilamellar liposomes (MLVs and LUVs). The distinction between optical properties of MLS- and LUVs-derived H phase, provided from turbidity-sensitive temperature-dependent UV-Vis spectra, was attributed to different formation mechanisms of H phase. Most importantly, from FTIR spectroscopic data of POPE lipids in L (15 °C), L (50 °C) and H (85 °C) phases we identified the changes in molecular features of POPE lipids during phase transitions. Among the latter, by far the most significant is different hydration pattern of POPE lipids in MLVs- and LUVs-derived H phase which extends from the polar-apolar interface all the way to the terminal amino group of the POPE lipid, along with the changes in the conformation of glycerol backbone as evidenced by the signature of α-methylene groups. Molecular dynamics simulations confirmed higher water penetration in H phase and provided insight into hydrogen bonding patterns.

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http://dx.doi.org/10.1016/j.saa.2024.124462DOI Listing

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