FIGURE 5.
Schematic representation of DPPC monolayers with PMI-COOH molecules. (A) The electrical field generated by the transition-induced dipole moment of the dye ( green arrow) determines an induced dipole moment in the polarizable molecule placed in its vicinity (
blue arrow). The resulting transition dipole moment of the dye (
red arrow) is the sum of the two vectors and has smaller amplitude. (B) Lo phase. Due to the tight packing of molecules in this phase, a cholesterol molecule (representing the polarizable element) was placed near a PMI-COOH molecule. (C) The calculated decay time variation when cholesterol is placed near PMI-COOH, as a function of distance. The line is drawn at a distance of ∼4 Å between the centers of the molecules; smaller values are less probable due to steric effects. At a distance of 5 Å from PMI-COOH, the cholesterol molecule produces an increase in the dye lifetime of ≈1.3 times, comparable with the experimental value. (D) Ld phase. Because of the less tight packing of the molecules in this phase and of the presence of a high proportion of free volume (∼40% as demonstrated in molecular dynamics simulation studies (67)), a void is placed near the dye. This does not influence the decay time of PMI-COOH.