Macromolecules, Vol.35, No.25, 9497-9505, 2002
Nonradiative excitation energy transfer in hydrophobically modified amphiphilic block copolymer micelles. theoretical model and Monte Carlo simulations
A general approach for analyzing the direct nonradiative excitation transfer from donors to traps (NRET) in systems of specifically tagged polymeric micelles is presented. We assume that the micelles are formed by a hydrophobic/hydrophilic diblock copolymer in a strongly polar selective solvent. The micelle-forming chain is tagged by a donor between blocks and by a strongly hydrophobic trap at the end of the hydrophilic shell-forming block. When micelles are formed the donors are trapped at the core/ shell interface and the hydrophobic traps try to avoid the polar medium and return back into the shell. Formation of compact chain conformations or loops is entropically unfavorable and the spatial distribution of traps in the shell is a result of the enthalpy-to-entropy interplay. Several physically reasonable but simplified models for the distributions of traps in the shell have been studied in detail. Representative results of computer-based Monte Carlo simulations of the time-resolved donor fluorescence decay as affected by NRET are presented for these systems. Comparison of our calculated and experimental curves allows us to. evaluate the distribution of traps in micellar shells of double-tagged micelles.