ABSTRACT
Assessment of chloroplast movements by measuring changes in leaf transmittance is discussed, with special reference to the conditions necessary for reliable estimation of blue light-activated chloroplast responses.
ABSTRACT
Fluorescence properties and trans-cis photoisomerisation of the benzoxazole derivatives 2-[4-(E)-(styryl)phenyl]benzoxazole (I), 2-{4-[(E)-2-(4-methoxyphenyl)vinyl]phenyl}benzoxazole (II), {4-[(E)-2-(4-benzoxazol-2-yl-phenyl)vinyl]phenyl}dimethylamine (III) and {4-[(E)-2-(4-benzoxazol-2-yl-phenyl)vinyl]phenyl}diphenylamine (IV) have been investigated in solvents of different polarities. It was found that these compounds exhibit efficient fluorescence with quantum yields and lifetimes strongly dependent on solvent polarity, although only compounds III and IV possess a significant charge transfer character in solvents of medium and high polarities. In addition, the photoisomerisation quantum efficiency depends strongly on the substitution of the phenyl ring in the electron donor moiety. A strong dependence of the quantum efficiency of the photoisomerisation on solvent was established. That quantity depends linearly on the non-radiative quantum yield of the deactivation of the excited singlet state for all investigated compounds. These results are consistent with a singlet state mechanism of the photoprocess. For compounds III and IV, with strong electron donors (N,N-dimethylaniline and triphenylamine), the molecule in the excited state trans configuration is more stabilized by solvent polarity than in the perpendicular form which causes more efficient isomerisation in nonpolar solvents. For compounds I and II the energy of the perpendicular configuration decreases more rapidly than that of the trans configuration when solvent polarity increases. In this case the energy barrier decreases with increasing solvent polarity. This makes the photoisomerisation process easier in polar solvents.
ABSTRACT
Geometry and vibrational modes of the anthranilic acid molecule in the S(0) and S(1) states were computed using ab initio methods: Hartree-Fock (HF) and configuration interaction of singly excited configurations (CIS) as well as the density functional theory with time-dependent perturbation (TD-DFT). The intensity distribution in the laser-induced fluorescence excitation spectra was modeled in two ways: using displacement parameters for independent modes and using multidimensional Franck-Condon integrals. The change in the molecular geometry upon excitation was calculated from the band intensities within the above two models. Displacement parameters of eight in-plane modes active in the excitation spectrum were optimized to reproduce the experimental intensities of about 40 most intensive and well-separated vibrational bands, while displacement parameters of other in-plane modes were kept frozen at the values resulting from the quantum chemical calculations. The intramolecular hydrogen bond is significantly stronger in the S(1) state than in the ground state. Additionally, bond lengths and angles in the aromatic ring, within the substituents and between the ring and the substituents undergo significant changes and they induce the presence of strong fundamentals in the excitation spectrum.