Impact of polymer chain packing and crystallization on the emission behavior of curcumin-embedded poly(L-lactide)s

The development of biodegradable and biocompatible fluorescent materials with tunable emission in the solid state has become increasingly relevant for smart packaging and biomedical applications. Molecular packing and conformations play a critical role in tuning the solid-state photophysical properties of fluorescent materials. In this work, tunable emission of bioactive curcumin was achieved through the manipulation of the crystallization conditions and the polymorphic form of covalently linked poly(L-lactide) in the curcumin-embedded poly(L-lactide) (curcumin-PLLA). In the melt-crystallized curcumin-PLLA, with the increase in the isothermal crystallization temperature, a bathochromic shift in the fluorescence of curcumin-PLLA was observed due to the change in the intramolecular conjugation length of curcumin. The change in the isothermal crystallization temperature of curcumin-PLLA resulted in the rotation of the terminal phenyl rings of curcumin with respect to the central keto-enol group due to the covalently linked helical PLLA chains. In addition, solvent-induced single crystals and a gel of curcumin-PLLA were prepared and the influence of the polymorphic form of PLLA on the emission behavior of curcumin-PLLA was investigated. The results suggest that the polymer chain packing, crystallization conditions, morphology, and polymorphic form could play an influential role in dictating the fluorescence properties of fluorophore-embedded polymers.