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- 5-Deazaalloxazine as photosensitizer of singlet oxygen and potential redox-sensitive agentPublication . Insińska-Rak, Małgorzata; Golczak, Anna; Gierszewski, Mateusz; Anwar, Zubair; Cherkas, Volodymyr; Kwiatek, Dorota; Sikorska, Ewa; Khmelinskii, Igor; Burdziński, Gotard; Cibulka, Radek; Mrówczyńska, Lucyna; Kolanowski, Jacek Lukasz; Sikorski, MarekFlavins are a unique class of compounds that combine the features of singlet oxygen generators and redox-dependent fluorophores. From a broad family of flavin derivatives, deazaalloxazines are significantly underdeveloped from the point of view of photophysical properties. Herein, we report photophysics of 5-deazaalloxazine (1a) in water, acetonitrile, and some other solvents. In particular, triplet excited states of 1ain water and in acetonitrile were investigated using ultraviolet-visible (UV-Vis) transient absorption spectroscopy. The measured triplet lifetimes for 1a were all on the microsecond time scale (approximate to 60 mu s) in deoxygenated solutions. The quantum yield of S-1 -> T-1 intersystem crossing for 1ain water was 0.43 based on T1 energy transfer from 1a to indicaxanthin (5) acting as acceptor and on comparative actinometric measurements using benzophenone (6). 1a was an efficient photosensitizer for singlet oxygen in aerated solutions, with quantum yields of singlet oxygen in methanol of about 0.76, compared to acetonitrile similar to 0.74, dichloromethane similar to 0.64 and 1,2-dichloroethane similar to 0.54. Significantly lower singlet oxygen quantum yields were obtained in water and deuterated water (Phi(Delta)similar to 0.42 and 0.44, respectively). Human red blood cells (RBC) were used as a cell model to study the antioxidant capacity in vitro and cytotoxic activity of 1a. Fluorescence-lifetime imaging microscopy (FLIM) data were analyzed by fluorescence lifetime parameters and distribution for different parts of the emission spectrum. Comparison of multidimensional fluorescent properties of RBC under physiological-like and oxidative-stress conditions in the presence and absence of 1a suggests its dual activity as probe and singlet-oxygen generator and opens up a pathway for using FLIM to analyze complex intracellular behavior of flavin-like compounds. These new data on structure-property relationship contribute to the body of information required for a rational design of flavin-based tools for future biological and biochemical applications.
- Photophysical properties of alloxazine derivatives with extended aromaticity – Potential redox-sensitive fluorescent probePublication . Golczak, Anna; Insińska-Rak, Małgorzata; Davoudpour, Amirali; Hama Saeed, Daban; Ménová, Petra; Mojr, Viktor; Cibulka, Radek; Khmelinskii, Igor; Mrówczyńska, Lucyna; Sikorski, MarekThe spectral and photophysical properties of two four-ring alloxazine derivatives, naphtho[2,3-g] pteridine-2,4(1H,3H)-dione (1a) and 1,3-dimethylnaphtho[2,3-g]pteridine-2,4(1H,3H)-dione, (1b) were studied. The propensity of 1a for excited-state proton transfer reactions in the presence of acetic acid as a catalyst was also studied, showing no signature of the reaction occurring. In addition, quenching of 1a fluorescence by acetic acid was investigated. Singlet and triplet states and spectral data for 1a and 1b were calculated using density functional theory TD-DFT at B3LYP/6-31G(d) and UB3LYP levels. Finally, fluorescence lifetime imaging microscopy (FLIM) using 1a and 1b as fluorescence probes was applied to in vitro human red blood cells (RBCs) with and without tert-butyl hydroperoxide (TB) as an oxidising agent. To evaluate and compare the effects of 1a and 1b on the redox properties of RBCs, the fluorescence lifetime, amplitude and fractional intensities were calculated, and phasor plot analysis was performed. The results obtained show the appearance of a new proximal cluster in the phasor fingerprint of RBCs in the presence of 1b and a shorter fluorescence lifetime of RBCs in the presence of 1a.