Electrical Properties of Membrane Phospholipids in Langmuir Monolayers

Chachaj-Brekiesz, Anna and Kobierski, Jan and Wnętrzak, Anita and Dynarowicz-Latka, Patrycja (2021) Electrical Properties of Membrane Phospholipids in Langmuir Monolayers. Membranes, 11 (1). p. 53. ISSN 2077-0375

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Abstract

Experimental surface pressure (π) and electric surface potential (ΔV) isotherms were measured for membrane lipids, including the following phosphatidylcholines (PCs)—1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC); 1,2-distearoyl-sn-glycero-3-phosphocholine (DSPC); 1,2-diarachidoyl-sn-glycero-3-phosphocholine (DAPC); and 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC). In addition, other phospholipids, such as phosphatidylethanolamines (represented by 1,2-dipalmitoyl-sn-glycero-3-phosphoethanolamine (DPPE)) and sphingolipids (represented by N-(hexadecanoyl)-sphing-4-enine-1-phosphocholine (SM)) were also studied. The experimental apparent dipole moments (μexpA) of the abovementioned lipids were determined using the Helmholtz equation. The particular contributions to the apparent dipole moments of the investigated molecules connected with their polar (μp⊥) and apolar parts (μa⊥) were theoretically calculated for geometrically optimized systems. Using a three-layer capacitor model, introducing the group’s apparent dipole moments (calculated herein) and adopting values from other papers to account for the reorientation of water molecules (μw⊥/εw), as well as the for the local dielectric permittivity in the vicinity of the polar (εp) and apolar (εa) groups, the apparent dipole moments of the investigated molecules were calculated (μcalcA). Since the comparison of the two values (experimental and calculated) resulted in large discrepancies, we developed a new methodology that correlates the results from density functional theory (DFT) molecular modeling with experimentally determined values using multiple linear regression. From the fitted model, the following contributions to the apparent dipole moments were determined: μw⊥/εw=−1.8±1.4 D; εp=10.2±7.0 and εa=0.95±0.52). Local dielectric permittivity in the vicinity of apolar groups (εa) is much lower compared to that in the vicinity of polar moieties (εp), which is in line with the tendency observed by other authors studying simple molecules with small polar groups. A much higher value for the contributions from the reorientation of water molecules (μw⊥/εw) has been interpreted as resulting from bulky and strongly hydrated polar groups of phospholipids.

Item Type: Article
Uncontrolled Keywords: Langmuir monolayers; electric surface potential; dipole moments; phospholipids
Subjects: STM Repository > Geological Science
Depositing User: Managing Editor
Date Deposited: 22 Jun 2023 05:24
Last Modified: 24 Oct 2024 04:00
URI: http://classical.goforpromo.com/id/eprint/1510

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