Femtosecond Fluorescence Upconversion Investigations on the Excited-State Photophysics of Curcumin

The demonstration of curcumin as a photodynamic therapy agent has generated a high level of interest in understanding the photoinduced chemical and physical properties of this naturally occurring, yellow-orange medicinal compound. Important photophysical processes that may be related to photodynamic therapy effects including excited-state intramolecular hydrogen atom transfer (ESIHT) occur within the femtosecond to picosecond time scales. Femtosecond fluorescence upconversion spectroscopy has sufficient time resolution to resolve and investigate these important photophysical processes. In this review, recent advances in using femtosecond fluorescence upconversion to reveal ultrafast solvation and ESIHT of curcumin are presented. The excited-state photophysics of curcumin has been investigated in alcohols and micellar solutions. The results of curcumin inmethanol and ethylene glycol reveal the presence of two decay components in the excited-state kinetics with time scales of 12–20 ps and,100ps. Similarly, in a micellar solution, biphasic kinetics are presentwith the fast decay component having a time constant of 3–8 ps, the slow decay component 50–80 ps. Deuteration of curcumin in both media leads to a pronounced isotope effect in the slow decay component, which suggests that ESIHT is an important photophysical process on this time scale. The results ofmultiwavelength fluorescence upconversion studies show that the fast component in the excited-state kinetics is due to ultrafast solvation. These advances form a part of the continuing efforts to elucidate the photodynamic therapy properties of curcumin.