Excited State Dynamics of Bis-Dehydroxycurcumin Tert-Butyl Ester, a Diketo-Shifted Derivative of the Photosensitizer Curcumin

PLoS One. 2017 Apr 27;12(4):e0175225. doi: 10.1371/journal.pone.0175225. eCollection 2017.

Abstract

Bis-dehydroxycurcumin tert-butyl ester (K2T23) is a derivative of the natural spice curcumin. Curcumin is widely studied for its multiple therapeutic properties, including photosensitized cytotoxicity. However, the full exploitation of curcumin phototoxic potential is hindered by the extreme instability of its excited state, caused by very efficient non radiative decay by means of transfer of the enolic proton to the nearby keto oxygen. K2T23 is designed to exhibit a tautomeric equilibrium shifted toward the diketo conformers with respect to natural curcumin. This property should endow K2T23 with superior excited-state stability when excited in the UVB band, i.e., in correspondence of the diketo conformers absorption peaks, making this compound an interesting candidate for topical photodynamic therapy of, e.g., skin tumors or oral infections. In this work, the tautomeric equilibrium of K2T23 between the keto-enolic and diketo conformers is assessed in the ground state in several organic solvents by UV-visible absorption and by nuclear magnetic resonance. The same tautomeric equilibrium is also probed in the excited-state in the same environments by means of steady-state fluorescence and time-correlated single-photon counting measurements. These techniques are also exploited to elucidate the excited state dynamics and excited-state deactivation pathways of K2T23, which are compared to those determined for several other curcuminoids characterized in previous works of ours. The ability of K2T23 in photosensitizing the production of singlet oxygen is compared with that of curcumin.

MeSH terms

  • Carboxylic Acids / chemistry
  • Curcumin / analogs & derivatives
  • Curcumin / chemistry*
  • Isomerism
  • Photons
  • Photosensitizing Agents / chemistry*

Substances

  • Carboxylic Acids
  • Photosensitizing Agents
  • bis-dehydroxycurcumin tert-butyl ester
  • Curcumin

Grant support

The authors received no specific funding for this work.