Photo-physics study of an hydroxy-quinoline derivative as inhibitor of Pim-1 kinase: ultraviolet-visible linear dichroism spectroscopy and quantum chemical calculations.

The photophysical properties of the antiviral 7-nicotinoyl-styrylquinoline (MB96) were investigated by means of UV-Vis linear dichroism (LD) spectroscopy on molecular samples aligned in stretched polyvinylalcohol (PVA), supported by time dependent density functional theory (TD-DFT) calculations. Experimentally, the directions of the transitions moments with respect to the long axis of the molecule were deduced from the orientation K factors, determined by means of "trial-and-error" procedure. The absorption spectrum presents two parts. The main transition in the lowest energy part, observed around 365 nm and showing the highest K value 0.8, is longitudinally in-plane polarized. The highest energy part which is extended between 230 and 320 nm, large, diffuse, and of weak intensity, shows estimated K values between 0.2 and 0.5. This complex structure is transversally polarized with some contamination by the longitudinal character of the first strong band. The TD-DFT results agree fairly well with the LD measurements.

Vibrations of the phenoxyl radical.

Phenoxyl radical (C(6)H(5)O) was prepared photochemically in low-temperature argon matrices. The infrared absorption spectra were obtained for C(6)H(5)O and for the isotopically labeled species C(6)D(5)O and 1-(13)C(12)C(5)H(5)O. All but one IR-active fundamental vibrations were detected, most of them not previously observed. Combination of results from IR linear dichroism measurements on photooriented samples, determination of absolute IR intensities with the help of internal standards, analysis of isotopic shifts, and quantum chemical predictions (B3LYP/cc-pVTZ) led to a detailed assignment of phenoxyl radical vibrations. Significant frequency shifts are observed with respect to previously reported data based on resonance Raman studies in polar solutions. For some vibrations, these shifts reflect environment-induced structural changes, such as increase of the quinoid character of the phenoxyl radical in polar media. In particular, the frequency of the CO stretching vibration, readily observable in both IR and Raman experiments, is extremely sensitive to the environment and can thus be used to probe its polarity.

Interaction between ellagic acid and calf thymus DNA studied with flow linear dichroism UV-VIS spectroscopy.

The interaction between ellagic acid and DNA has been characterized with respect to the geometry of the ellagic acid-DNA complex, and the active form of ellagic acid has been identified. Optical spectroscopic methods have been employed to examine the interaction between double-stranded calf thymus DNA and ellagic acid in low-ionic-strength aqueous solutions at pH values of 5.5, 7.0, and 8. 8. Based on normal absorption titration and flow linear dichroism experiments, it is confirmed that the neutral form of ellagic acid present at pH 5.5 binds to double-stranded DNA. It is found that the plane of the ellagic acid chromophore is positioned at an angle relative to the DNA helix axis, which is in accordance with intercalation of ellagic acid in DNA. It is concluded that at higher values of pH no or a very limited amount of ellagic acid binds to DNA. These results prove that the direct interaction between ellagic acid and DNA must be taken into account when evaluating the mechanism underlying the observed biological effects of this plant phenol.