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Lipid spontaneous curvatures estimated from temperature-dependent changes in inverse hexagonal phase lattice parameters: effects of metal cations

Lipid spontaneous curvatures estimated from temperature-dependent changes in inverse hexagonal phase lattice parameters: effects of metal cations
Lipid spontaneous curvatures estimated from temperature-dependent changes in inverse hexagonal phase lattice parameters: effects of metal cations
Recently we reported a method for estimating the spontaneous curvatures of lipids from temperature-dependent changes in the lattice parameter of inverse hexagonal liquid crystal phases of binary lipid mixtures. This method makes use of 1,2-dioleoyl-sn-glycerol-3-phosphoethanolamine (DOPE) as a host lipid, which preferentially forms an inverse hexagonal phase to which a guest lipid of unknown spontaneous curvature is added. The lattice parameters of these binary lipid mixtures are determined by small-angle X-ray diffraction at a range of temperatures and the spontaneous curvature of the guest lipid is determined from these data. Here we report the use of this method on a wide range of lipids under different ionic conditions. We demonstrate that our method provides spontaneous curvature values for DOPE, cholesterol, and monoolein that are within the range of values reported in the literature. Anionic lipids 1,2-dioleoyl-sn-glycerol-3-phosphatidic acid (DOPA) and 1,2-dioleoyl-sn-glycerol-3-phosphoserine (DOPS) were found to exhibit spontaneous curvatures that depend on the concentration of divalent cations present in the mixtures. We show that the range of curvatures estimated experimentally for DOPA and DOPS can be explained by a series of equilibria arising from lipid-cation exchange reactions. Our data indicate a universal relationship between the spontaneous curvature of a lipid and the extent to which it affects the lattice parameter of the hexagonal phase of DOPE when it is part of a binary mixture. This universal relationship affords a rapid way of estimating the spontaneous curvatures of lipids that are expensive, only available in small amounts, or are of limited chemical stability.
0743-7463
10083-10092
Dymond, Marcus K.
e180765b-039e-47ff-9841-ce6a5123a519
Gillams, Richard
89341fe4-db94-4d27-a5be-c092e2e8de5b
Parker, Duncan
37b1d9c5-0e8a-42f4-b9ad-56e33d61e781
Burrell, James
23629bf3-31aa-4d14-b988-d2612999c00c
Labrador, Ana
2b101823-33e1-4e2b-9271-e4ba186ab17d
Nylander, Tommy
18d94ea0-6456-4eaf-b552-844261a37283
Attard, George
3219075d-2364-4f00-aeb9-1d90f8cd0d36
Dymond, Marcus K.
e180765b-039e-47ff-9841-ce6a5123a519
Gillams, Richard
89341fe4-db94-4d27-a5be-c092e2e8de5b
Parker, Duncan
37b1d9c5-0e8a-42f4-b9ad-56e33d61e781
Burrell, James
23629bf3-31aa-4d14-b988-d2612999c00c
Labrador, Ana
2b101823-33e1-4e2b-9271-e4ba186ab17d
Nylander, Tommy
18d94ea0-6456-4eaf-b552-844261a37283
Attard, George
3219075d-2364-4f00-aeb9-1d90f8cd0d36

Dymond, Marcus K., Gillams, Richard, Parker, Duncan, Burrell, James, Labrador, Ana, Nylander, Tommy and Attard, George (2016) Lipid spontaneous curvatures estimated from temperature-dependent changes in inverse hexagonal phase lattice parameters: effects of metal cations. Langmuir, 32 (39), 10083-10092. (doi:10.1021/acs.langmuir.6b03098).

Record type: Article

Abstract

Recently we reported a method for estimating the spontaneous curvatures of lipids from temperature-dependent changes in the lattice parameter of inverse hexagonal liquid crystal phases of binary lipid mixtures. This method makes use of 1,2-dioleoyl-sn-glycerol-3-phosphoethanolamine (DOPE) as a host lipid, which preferentially forms an inverse hexagonal phase to which a guest lipid of unknown spontaneous curvature is added. The lattice parameters of these binary lipid mixtures are determined by small-angle X-ray diffraction at a range of temperatures and the spontaneous curvature of the guest lipid is determined from these data. Here we report the use of this method on a wide range of lipids under different ionic conditions. We demonstrate that our method provides spontaneous curvature values for DOPE, cholesterol, and monoolein that are within the range of values reported in the literature. Anionic lipids 1,2-dioleoyl-sn-glycerol-3-phosphatidic acid (DOPA) and 1,2-dioleoyl-sn-glycerol-3-phosphoserine (DOPS) were found to exhibit spontaneous curvatures that depend on the concentration of divalent cations present in the mixtures. We show that the range of curvatures estimated experimentally for DOPA and DOPS can be explained by a series of equilibria arising from lipid-cation exchange reactions. Our data indicate a universal relationship between the spontaneous curvature of a lipid and the extent to which it affects the lattice parameter of the hexagonal phase of DOPE when it is part of a binary mixture. This universal relationship affords a rapid way of estimating the spontaneous curvatures of lipids that are expensive, only available in small amounts, or are of limited chemical stability.

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More information

Accepted/In Press date: 21 August 2016
e-pub ahead of print date: 7 September 2016
Published date: 4 October 2016
Organisations: Computational Systems Chemistry

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Local EPrints ID: 402210
URI: http://eprints.soton.ac.uk/id/eprint/402210
ISSN: 0743-7463
PURE UUID: 5065f980-9cfa-4ca8-9bf6-439775bd6dc4
ORCID for Richard Gillams: ORCID iD orcid.org/0000-0002-8597-8723
ORCID for George Attard: ORCID iD orcid.org/0000-0001-8304-0742

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Date deposited: 03 Nov 2016 15:09
Last modified: 07 Oct 2020 05:45

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