Dataset Information

Headgroup-Ordered Monolayers of Uncharged Glycolipids Exhibit Selective Interactions with Ions.

ABSTRACT: Selective interactions of ions with charge-neutral saccharides can have far-reaching consequences in biological and wet-technological contexts but have so far been observed only indirectly. Here, we directly quantify by total-reflection X-ray fluorescence the preferential accumulation of ions near uncharged saccharide surfaces in the form of glycolipid Langmuir monolayers at air/water interfaces exhibiting different levels of structural ordering. Selective interactions with ions from the aqueous subphase are observed for monolayers featuring crystalline ordering of the saccharide headgroups, as determined by grazing-incidence X-ray diffraction. The attracted ion species depend on the structural motifs displayed by the ordered saccharide layer. Our results may constitute a basis to understand the salt-specific swelling of wood materials and various phenomena in membrane biophysics.

SUBMITTER: Stefaniu C

PROVIDER: S-EPMC6727371 | biostudies-literature | 2019 Apr

REPOSITORIES: biostudies-literature

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Headgroup-Ordered Monolayers of Uncharged Glycolipids Exhibit Selective Interactions with Ions.

Stefaniu Cristina C Latza Victoria M VM Gutowski Olof O Fontaine Philippe P Brezesinski Gerald G Schneck Emanuel E

The journal of physical chemistry letters 20190327 8

Selective interactions of ions with charge-neutral saccharides can have far-reaching consequences in biological and wet-technological contexts but have so far been observed only indirectly. Here, we directly quantify by total-reflection X-ray fluorescence the preferential accumulation of ions near uncharged saccharide surfaces in the form of glycolipid Langmuir monolayers at air/water interfaces exhibiting different levels of structural ordering. Selective interactions with ions from the aqueous ...[more]

PMID: 30908061

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Project description:Ceramide is a major actor in the sphingolipid signaling pathway elicited by various kinds of cell stress. Under those conditions ceramide (Cer) is produced in the plasma membrane as a product of sphingomyelin (SM) hydrolysis, and this may lead to apoptosis. Thus, SM and Cer coexist in the membrane for some time, and they are known to separate laterally from the (more abundant) glycerolipids, giving rise to highly rigid domains or platforms. The properties of these domains/platforms are rather well understood, but the underlying SM:Cer molecular interactions have not been explored in detail. Infrared (IR) spectroscopy is a powerful analytical technique that provides information on all the chemical groupings in a molecule, and that can be applied to membranes and lipid bilayers in aqueous media. IR spectra can be conveniently retrieved as a function of temperature, thus revealing the thermotropic transitions of SM and its mixtures with Cer. Four regions of the IR spectrum of these sphingolipids have been examined, two of them dominated by the hydrophobic regions in the molecules, namely the C-H stretching vibrations (2800-3000 cm-1), and the CH2 scissoring vibrations (1455-1485 cm-1), and two others arising from chemical groups at the lipid-water interface, the sphingolipid amide I band (1600-1680 cm-1), and the phosphate vibrations in the 1000-1110 cm-1 region. The latter two regions have been rarely studied in the past. The IR data from the hydrophobic components show a gel (or ripple)-fluid transition of SM at 40 °C, that is shifted up to about 70 °C when Cer is added to the bilayers, in agreement with previous studies using a variety of techniques. IR information concerning the polar parts is more interesting. The amide I (carbonyl) band of pure SM exhibits a maximum at 1638 cm-1 at room temperature, and its position is shifted by about 10 cm-1 in the presence of Cer. Cer causes also a change in the overall band shape, but no signs of band splitting are seen, suggesting that SM and Cer carbonyl groups are interacting tightly, presumably through H-bonds. The 1086 cm-1 band, corresponding to PO2- vibrations, appears more stable in SM than in DPPC, and it is further stabilized by Cer, again suggesting an important role of H-bonds in the formation of SM:Cer clusters. Thus, SM and Cer can interact through their polar headgroups, in a way that is not accessible to other lipid classes.

Dataset Information

Headgroup-Ordered Monolayers of Uncharged Glycolipids Exhibit Selective Interactions with Ions.

Publications

Headgroup-Ordered Monolayers of Uncharged Glycolipids Exhibit Selective Interactions with Ions.

Similar Datasets

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