Excited State Photophysics of Curcumin and its Modulation in Alkaline Non‐Aqueous Medium

• Published in: Chemphyschem 2023-08, Vol.24 (16), p.e202300174-n/a
• Main Authors: Ghosh, Meghna, Parida, Sanjukta, Khatoon, Huma, Bera, Nanigopal, Mishra, Sabyashachi, Sarkar, Nilmoni
• Format: Article
• Language: English
• Subjects: alkaline non-aqueous medium; Aqueous solutions; binary mixture; Biomolecules; Charge transfer; curcumin; Density functional theory; deprotonation; Dynamics; Excitation; Fluorescence; Protons; Solvation; Solvents; Time dependence; time-resolved spectroscopy
• ISSN: 1439-4235; 1439-7641
• DOI: 10.1002/cphc.202300174

Curcumin, a well‐known medicinal pigment, has seen limited applications in biology despite having great potential as a therapeutic drug. Deprotonation is one of the possible ways to enhance solubility of curcumin in polar solvent. Here, we have explored the effect of deprotonation on the ultrafast dynamics of this biomolecule with the help of the time‐resolved fluorescence spectroscopic measurements using the femtosecond fluorescence upconversion technique. The excited state photophysics of fully deprotonated curcumin significantly differs from that of neutral curcumin. We have observed that the completely deprotonated curcumin not only has higher quantum yield, but also higher excited state lifetime and slower solvation dynamics in comparison to neutral curcumin. We propose solvation dynamics and intramolecular charge transfer as the excited state processes associated with the radiative decay of the completely deprotonated molecule, while ruling out the possibility of excited state proton exchange or proton transfer. Our results are well supported by time‐dependent density‐functional theory calculations. Lastly, we have also demonstrated the possibility of modulating the ultrafast dynamics of fully deprotonated curcumin using non‐aqueous alkaline binary solvent mixtures. We believe our results will provide significant physical insight towards unveiling the excited state dynamics of this molecule. Fully deprotonated curcumin shows unexpected photophysical properties in non‐aqueous medium, which have been elucidated using time‐resolved fluorescence spectroscopy and time‐dependent density‐functional theory.