Thermal characterization of poly(ethylene glycol)-poly(D,L-lactide) block copolymer micelles based on pyrene excimer formation.

Poly(ethylene glycol)--poly(D,L-lactide) (PEG-PDLLA) block copolymers were prepared by anionic ring-opening polymerization, resulting in block sizes effectively controlled by initial monomer/initiator ratios and low molecular weight distributions (<1.12). A pyrene derivative (1-pyrenyl carbonyl cyanide--Py) was conjugated to the end of the hydrophobic block (PDLLA) in a quantitative manner, with coupling efficiencies >95%. The so-obtained PEG-PDLLA-Py copolymers displayed fluorescent properties that were associated with the pyrene monomers, when placed in good solvents for both the hydrophilic and hydrophobic blocks. When placed in selective solvents, these copolymers self-assembled into micelles in the 30-nm range, also with low particle size distributions (<0.09), within which Py could be readily entrapped in the hydrophobic PDLLA core. Py entrapment resulted in the formation of excimers, as evident from fluorescence measurements. Observation of excimer formation/dissociation further conveyed information on the physicochemical properties of the core. Thermal characterization of these systems showed that an increase in the temperature resulted in changes in the properties of excimer fluorescence, an occurrence attributed to a higher mobility of the otherwise glassy PDLLA. This, in turn, greatly affected the inter-molecular distance between pyrene molecules, a crucial factor for excimer formation. The glass transition of the PDLLA block, approximately 38 degrees C, defined the onset for increasing chain mobility and whence excimer dissociation. Excimer fluorescence appeared to be time-dependent. Based on these observations, chain exchange processes were clearly evidenced through the time-dependent dissociation of excimers into unimers, a process that was influenced by changes in temperature.