Fluorination of the hydrophilic head accelerates the collapse of the monolayer but stabilizes the bilayer of a long-chain trifluoroethyl ether on water
A comparison of the collapse of Langmuir monolayers of docosyl trifluoroethyl ether (DFEE) and docosyl ethyl ether (DEE) on water shows that in both films the 3D phase is formed layer-by-layer. The substitution of CH3 by a CF3 group in the hydrophilic head yields a more stable bilayer exhibiting low...
| Veröffentlicht in: | Langmuir : the ACS journal of surfaces and colloids. - 1992. - 22(2006), 9 vom: 25. Apr., Seite 4136-43 |
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| Weitere Verfasser: | , |
| Format: | Aufsatz |
| Sprache: | English |
| Veröffentlicht: |
2006
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| Zugriff auf das übergeordnete Werk: | Langmuir : the ACS journal of surfaces and colloids |
| Schlagworte: | Journal Article |
| Zusammenfassung: | A comparison of the collapse of Langmuir monolayers of docosyl trifluoroethyl ether (DFEE) and docosyl ethyl ether (DEE) on water shows that in both films the 3D phase is formed layer-by-layer. The substitution of CH3 by a CF3 group in the hydrophilic head yields a more stable bilayer exhibiting lower equilibrium spreading pressure, pi(esp)(DFEE) < pi(esp)(DEE). Upon lateral compression, the DFEE bilayer fractures abruptly as a compact solid body whereas the DEE bilayer breaks down gradually as a polycrystalline material. A comparison of the collapse kinetics of the two films at the same constant supersaturation pi-pi(esp) = 7 mN/m shows that the fluorinated DFEE monolayer transforms more quickly, yielding a stable bilayer of closely packed upright molecules, whereas the DEE film undergoes a continuous monolayer-bilayer-multilayer transition. Brewster angle microscopy allows us to visualize different collapse mechanisms of the DFEE and DEE films; the domains of the fluorinated DFEE bilayer grow laterally at constant thickness and density, and the collapse of the nonfluorinated DEE monolayer occurs through a sequence of disordered stripelike and broken elongated textures. The characteristic molecular areas of the monolayer and bilayer collapse suggest that the 2D-3D transition in the DFEE and DEE films is accompanied by at least partial dehydration of their headgroups. The faster collapse of the fluorinated monolayer could result from a lower energy barrier due to the more hydrophobic CF3 group in the heads. The increased stability of the DFEE bilayer could be associated with the electrostatic attraction between the -C(F delta-)3 versus (H delta+)3C- terminals at the heads-to-tails contact plane of the top and the bottom layer, contrasting with the repulsion between the -C(H delta+)3 versus (H delta+)3C- terminals of the top-layer heads and the bottom-layer tails in the DEE bilayer |
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| Beschreibung: | Date Completed 03.07.2007 Date Revised 18.04.2006 published: Print Citation Status PubMed-not-MEDLINE |
| ISSN: | 1520-5827 |