Lamine Cisse

Quantitative treatment of the effect of solvent on the electronic absorption and fluorescence spectra of substituted coumarins: Evaluation of the first excited singlet-state dipole moments.

The electronic absorption and fluorescence spectra of coumarin and 11 substituted coumarins were measured in several solvents (dioxane, ethyl ether, ethyl acetate, ethanol, dimethylformamide, acetonitrile, and dimethyl sulfoxide). Ground-state dipole moments were determined in dioxane at 298 K. The results were used to obtain the first excited singlet-state dipole moments of the coumarins under study by the solvatochromic shift method (Bakhshiev, Kawski-Chamma-Viallet, McRae, and Suppan correlations). Also, the ground- and the first excited singlet-state dipole moments were calculated using a combination of the PPP method (π-contribution) and the vector sum of the σ-bond and group moments (σ-contribution). In general, the first excited singlet-state dipole moments of the coumarins are noticeably higher than the corresponding ground-state values, indicating a substantial redistribution of theπ-electron densities resulting in a more polar excited state. There is a reasonably good agreement between the calculated and the experimental dipole moments.

Revisiting the photophysical properties and excited singlet-state dipole moments of several coumarin derivatives

The solvent effects on the electronic absorption and fluorescence emission spectra of several coumarins derivatives, containing amino, N,N-dimethyl-amino, N,N-diethyl-amino, hydroxyl, methyl, carboxyl, or halogen substituents at the positions 7, 4, or 3, were investigated in eight solvents with various polarities. The first excited singlet-state dipole moments of these coumarins were determined by various solvatochromic methods, using the theoretical ground-state dipole moments which were calculated by the AM1 method. The first excited singlet-state dipole moment values were obtained by the Bakhshiev, Kawski-Chamma-Viallet, Lippert-Mataga, and Reichardt-Dimroth equations, and were compared to the ground-state dipole moments. In all cases, the dipole moments were found to be higher in the excited singlet-state than in the ground state because of the different electron densities in both states. The red-shifts of the absorption and fluorescence emission bands, observed for most compounds upon increasing the solvent polarity, indicated that the electronic transitions were of π-π* nature.

Mass Spectrometry Study of Coumarins: Correlation Between Charges of Atoms and Fragmentation Processes

ABSTRACT The mass spectrometry of a number of 6-substituted coumarins was studied in the context of correlating fragmentation pathways and electronic charges of atoms performed by AM1 semiempirical method. The atomic charges of atoms are found to be good predictors of the fragmentation pathways.

Fluorescence Quenching of Two Coumarin-3-carboxylic Acids by Trivalent Lanthanide Ions

The effects of various trivalent lanthanide ions (acetates of Ce3+, Er3+, Eu3+, Nd3+) on the electronic absorption and fluorescence spectra of un-substituted coumarin-3-carboxylic acid (CCA) and 7-N,N-diethylamino-coumarin-3-carboxylic acid (DECCA) have been investigated in dimethylsulfoxide (DMSO) at room temperature. Depending on the lanthanide ion nature and concentration, significant spectral changes of absorption bands occurred for both coumarin derivatives. These spectral changes were attributed to the formation of ground-state complexes between the coumarin carboxylate derivatives and lanthanide ions. The fluorescence quenching of CCA and DECCA upon increasing the lanthanide ion concentration was studied. Different quantitative treatments, including the Stern-Volmer equation, the Perrin equation and a polynomial equation, were applied and compared in order to determine the nature of the quenching mechanisms for both coumarin derivatives. The results suggested the contribution of both dynamic and static quenching. Significant differences of CCA and DECCA fluorescence quenching efficiency were also observed, depending on the lanthanide ion. DECCA fluorescence lifetime measurements, performed in the absence and in the presence of Ln3+, confirmed a contribution of static quenching.

Spectrofluorometric Determination of Putrescine: Optimization of the Putrescine-Orthophthaldehyde Complex Using Spectrofluorometry.

In alkaline medium, the complex formed between putrescine and orthophthalaldehyde was studied using spectrofluorescence. The derivative is kinetically stable 24 h after complexation. The stoichiometry of the complex is 1:1 at maximum fluorescence intensity, also 24 h after complexation.

Light effects on Carbofuran and Fluometuron: Impact on natural waters. Spectrophotometric study

The aim of this work is to study the effect of light on Carbofuran and Fluometuron in various solvents, and to assess their ability to contaminate surface and ground waters. The results of this study show that these products are notoriously unstable under the effect of irradiation. Using water as solvent, we observed that the photodegradation rate of these products was slow, so they can lead to surface waters contamination. It was also observed that the photodegradation of Carbofuran in water was pH dependent. Indeed, Carbofuran is stable in neutral and acidic media, but undergoes photodegradation in basic medium. The kinetics of photodegradation showed that Fluometuron was first order kinetics in all solvents used, while for Carbofuran the kinetics was zero order reaction in the same solvents. Thus, at low concentrations, photodegradation of Carbofuran took place, very quickly. The measurements of the infiltration rate of these two products showed high mobility in the soil. For Carbofuran, the infiltration rate was 0.88 cm/min, and for Fluometuron it was 0.66 cm/min. As a result, these products can contaminate groundwater.