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Article Dans Une Revue Soft Matter Année : 2011

Insertion properties of cholesterylcyclodextrins in phospholipid membranes: a molecular study

Résumé

Amphiphilic cyclodextrins (CDs) are good candidates to functionalize natural membranes, as well as synthetic vesicles. In this paper, we fully describe and compare the insertion properties of the permethylated mono-cholesteryl α-CD (TASC) and its mono- and di-cholesteryl β-CD analogues (TBSC and TBdSC) in dipalmitoyl-L-α-phosphatidylcholine (DPPC) mono- and bi-layers as membrane models from the macroscopic to the molecular scale. By calculating the inverse compressibility moduli and free excess Gibbs energies from the Langmuir isotherms, the influence of the CD type, CD ratio and number of cholesteryl anchors on the membrane properties have been established. TBdSC, with its two cholesteryl residues, seems to be anchored best to the membrane compared to CD derivatives with only one anchor. Furthermore, TASC appears to be more firmly inserted into the membrane than TBSC. The in-plane structure is characterized by Brewster angle microscopy (BAM) at the air–water interface and atomic force microscopy (AFM) of the mono- and bi-layers deposited on mica. Depending on the compression, full miscibility of the cholesteryl CDs and the phospholipids is observed at low surface pressures and a clear demixing tendency is apparent during compression. CD-modified bilayers are stable and are subject to a gel–liquid phase transition upon heating. Due to their bulky CD moiety, the amphiphilic CDs exhibit a distinct fluidizing effect, shifting the DPPC's gel–liquid transition. The structure of the mixed TASC/DPPC mono- and bi-layers perpendicular to the surface is investigated with Ångstrom resolution by neutron reflectivity. In this way a molecular model of the insertion has been established, which suggests that the CD cavities partly protrude into the subphase, which should leave them accessible for complex formation.
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Dates et versions

hal-02301210 , version 1 (30-09-2019)

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Martin Bauer, Thierry Charitat, Christophe Fajolles, Giovanna Fragneto, Jean Daillant. Insertion properties of cholesterylcyclodextrins in phospholipid membranes: a molecular study. Soft Matter, 2011, 8 (4), pp.942-953. ⟨10.1039/c1sm06346d⟩. ⟨hal-02301210⟩
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