Alkylation converts riboflavin into an efficient photosensitizer of phospholipid membranes.

A new decyl chain [-(CH2)9CH3] riboflavin conjugate has been synthesized and investigated. A nucleophilic substitution (SN2) reaction was used for coupling the alkyl chain to riboflavin (Rf), a model natural photosensitizer. As expected, the alkylated compound (decyl-Rf) is significantly more lipophilic than its precursor and efficiently intercalates within phospholipid bilayers, increasing its fluorescence quantum yield. The oxidative damage to lipid membranes photoinduced by decyl-Rf was investigated in large and giant unilamellar vesicles (LUVs and GUVs, respectively) composed of different phospholipids. Using a fluorogenic probe, fast radical formation and singlet oxygen generation was demonstrated upon UVA irradiation in vesicles containing decyl-Rf. Photosensitized formation of conjugated dienes and hydroperoxides, and membrane leakage in LUVs rich in poly-unsaturated fatty acids were also investigated. The overall assessment of the results shows that decyl-Rf is a significantly more efficient photosensitizer of lipids than its unsubstituted precursor and that the association to lipid membranes is key to trigger phospholipid oxidation. Alkylation of hydrophilic photosensitizers as a simple and general synthetic tool to obtain efficient photosensitizers of biomembranes, with potential applications, is discussed.

Spectral characteristics and photosensitization of TiO2 nanoparticles in reverse micelles by perylenes.

We report on the photosensitization of titanium dioxide nanoparticles (TiO2 NPs) synthesized inside AOT (bis(2-ethylhexyl) sulfosuccinate sodium salt) reverse micelles following photoexcitation of perylene derivatives with dicarboxylate anchoring groups. The dyes, 1,7-dibromoperylene-3,4,9,10-tetracarboxy dianhydride (1), 1,7-dipyrrolidinylperylene-3,4,9,10-tetracarboxy dianhydride (2), and 1,7-bis(4-tert-butylphenyloxy)perylene-3,4,9,10-tetracarboxy dianhydride (3), have considerably different driving forces for photoinduced electron injection into the TiO2 conduction band, as estimated by electrochemical measurements and quantum mechanical calculations. Fluorescence anisotropy measurements indicate that dyes 1 and 2 are preferentially solubilized in the micellar structure, creating a relatively large local concentration that favors the attachment of the dye to the TiO2 surface. The binding process was followed by monitoring the hypsochromic shift of the dye absorption spectra over time for 1 and 2. Photoinduced electron transfer from the singlet excited state of 1 and 2 to the TiO2 conduction band (CB) is indicated by emission quenching of the TiO2-bound form of the dyes and confirmed by transient absorption measurements of the radical cation of the dyes and free carriers (injected electrons) in the TiO2 semiconductor. Steady state and transient spectroscopy indicate that dye 3 does not bind to the TiO2 NPs and does not photosensitize the semiconductor. This observation was rationalized as a consequence of the bulky t-butylphenyloxy groups which create a strong steric impediment for deep access of the dye within the micelle structure to reach the semiconductor oxide surface.

Estimation of the solvent reorganization energy and the absolute energy of solvation of charge-transfer states from their emission spectra.

We report herein the solvent and temperature effects on the emission of the intermolecular exciplexes 1-cyanonaphthalene/triethylamine and 1-methylnaphthalene/triethylamine and the intramolecular exciplexes formed by the bichromophoric compounds diethyl-(3-naphthalen-1-yl-propyl)-amine (I), diethyl-(2-naphthalen-1-yl-ethyl)-amine (II), 3-[ethyl-(2-naphthalen-1-yl-ethyl)-amino]-propionitrile (III) and 3-[(2-cyano-ethyl)-(2-naphthalen-1-yl-ethyl)-amino]-propionitrile (IV). The results are interpreted within the formalism of the semiclassical Marcus theory for radiative back electron transfer (BET) reactions. We show that, following a few simple assumptions, reliable values of the Gibbs free energy changes (DeltaG(epsilon)(-et)) and the solvent reorganization energies (lambda(epsilon)(s)) associated to the BET reactions (and their corresponding enthalpic and entropic contributions) can be estimated directly from the emission of the CT states. We also show that for the 1-cyanonaphthalene/triethylamine exciplex, which exhibits emission in the vapour phase, the experimental calculation of the absolute energy of solvation of the CT state (DeltaG(epsilon)(s)) is also possible. The calculated DeltaG(epsilon)(-et) correlate quite satisfactorily with the corresponding values obtained from independent electrochemical and kinetics experiments. The temperature effects on DeltaG(epsilon)(-et), lambda(epsilon)(s) and DeltaG(epsilon)(s) are discussed qualitatively using different solvation models. The limitations of the present approach for the estimation of DeltaG(epsilon)(-et) and lambda(epsilon)(s) and its possible application to more complex A/D systems are also examined.