1,32-DIHYDROXY-DOTRIACONTANE-BIS(RHODAMINE) 101 ESTER - A LIPID-MEMBRANE SPANNING BICHROMOPHORIC MOLECULE AS REVEALED BY INTRAMOLECULAR DONOR-DONOR ENERGY MIGRATION (DDEM)

The bichromophoric and monochromophoric probes, 1,32-dihydroxy-dotriac ontane-bis(Rhodamine) 101 ester (Rh101C(32)Rh101) and Rhodamine 101 oc tadecyl ester (Rh101C(18)), respectively, were solubilised in unilamel lar lipid vesicles of 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC), 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) and 1-palmitoyl-2- oleoyl-sn-glycero-3phosphocholine (POPC). At molar ratios of less than 1/5000 for Rh101C(18)/lipid and Rh101C(32)Rh101/lipid, intermolecular electronic energy migration is negligible, contrary to the intramolec ular donor-donor energy migration (DDEM) within the Rh101C(32)Rh101 mo lecules. The time-resolved fluorescence anisotropy determined for Rh10 1C(18) and Rh101C(32)Rh101 were globally analysed by using a recently developed model that accounts for reorientational motions, as well as the rate of DDEM (L. B-Angstrom. Johansson, F. Bergstrom, P. Edman, I. V. Grechishnikova and J. G. Molotkovsky, J. Chem. Soc., Faraday Trans ., 1996, 92, 1563). It was found that the rate of intramolecular DDEM within Rh101C(32)Rh101 is typically about 3 x 10(9) s(-1). In vesicles formed by DOPC and POPC, the distance between the Rhodamine groups of Rh101C(32)Rh101 is found to be about 35 Angstrom while it is about 32 Angstrom in DPPC vesicles. These values are in excellent agreement wi th reported thicknesses of the lipid bilayers. Thus, the present work strongly suggests that the Rh101C(32)Rh101 molecules are spanning acro ss the lipid bilayer, that is, the Rhodamine residues are located on o pposite sides of the lipid bilayer.