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Title
| - Hydraphile Channels: Structural and Fluorescent Probes of Positionand Function in a Phospholipid Bilayer
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Abstract
| - Three novel tris(macrocycle)s having fluorescent residues at their distal termini have been preparedand studied. The compounds are of the form R〈N18N〉C12〈N18N〉C12〈N18N〉R in which R is 2-(3-indolyl)ethyl (1), 2-(3-(N-methylindolyl))ethyl (2), and dansyl (3). Compounds 2 and 3 were found to transport Na+at rates similar to those of other tris(macrocyclic)s but 1 was not an ionophore in the bilayer as assessed by23Na NMR analysis. The latter failure may be due to a hydrogen-bond blockade leading to a globularconformation adopted by the hydraphile. The fluorescence maximum of 3 was determined in a variety ofsolvents and in a phospholipid bilayer. The polarity experienced by the dansyl group in the bilayer wasintermediate between that observed in methanol and ethanol. Fluorescence depth quenching using doxyl-substituted lipids showed that the dansyl headgroups of 3 were 14 Å from the bilayer's midplane or separatedby about 28 Å. Fluorescence energy transfer between 2 and 3 showed that these two hydraphiles were notappreciably aggregated in the bilayer.
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