Alphonse Tine

Determination of the First Excited Singlet State Dipole Moments of Coumarins by the Solvatochromic Method

Abstract The electronic absorption and fluorescence spectra of 4-hydroxycoumarin, 7-hydroxycoumarin, 7-methoxycoumarin, 7-hydroxy-4-methylcoumarin, 7-amino-4-methylcoumarin, and 7-diethylamino-4-methylcoumarin were measured at room temperature (298K) in several solvents and their first excited singlet-state dipole moments were determined by the solvatochromic shift method. The excited singlet-state dipole moments of the coumarins were compared with the ground-state values. ∗Presented, in part, at the 2nd International Conference on Solar Energy Storage and Applied Photochemistry, Cairo, Egypt, January 6—11, 1993.

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.

Effect of pH on the fluorescence and phosphorescence spectra of indolecarboxylic acids. Evidence for the existence of a singlet excited-state indole acid dianion☆

Abstract Room-temperature electronic absorption, fluorescence, and low-temperature (77 K) phosphorescence spectra of a series of indolecarboxylic acids have been measured in predominantly aqueous solutions at pH 1.2, 7.0, 12.5, and in 5 N NaOH. The 1 L a and 1 L b π, π ∗ states have been assigned to the electronic transitions for all the compounds under study. The quenching of fluorescence, the appearance of a new fluorescence emission band, red-shifted by 40 nm, in very alkaline media, and the disappearance of the indole carboxylate short-wavelength band have been attributed to the formation of an excited singlet-state indolate carboxylate (dianion) stabilized by hydrogen bonding with the solvent. The existence of two successive excited singlet-state prototropic equilibria is discussed.

Fluorimetric determination of histamine in fish using micellar media and fluorescamine as labelling reagent.

An analytical method based on the use of fluorescamine to produce a fluorescent derivative with histamine and combined with micellar-enhanced fluorescence detection of the formed complex is developed for the sensitive and rapid determination of histamine in fishes. The fluorescence properties of the obtained complex in water and micellar solutions of sodium dodecyl sulfate (SDS), cetyltrimethylammonium chloride (CTAC) and brij-700 are reported. Physicochemical variables influencing the sensitivity of the method (pH, micellar, fluorescamine and NaCl relative concentrations) have been optimized. The stability of the formed complex, as shown by kinetic study, depends on the pH of the solution. Linear calibration curves allowing an effective histamine determination were established with large linear dynamic range (LDR), and low limits of detection (LOD) between 0.5 and 33 ng mL-1, according to the solvent. Application to the analysis of fish samples (sardines) yielded satisfactory results. The method seems to be suitable for environmental fish quality control.

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.

Use a Fluorescent Molecular Sensor for the Detection of Pesticides and Herbicides in Water

A fluorescent chemosensor based on modified �-cyclodextrin was used for the detection of pesticides and her- bicides in water. Binding constants, thermodynamic parameters and sensitivity factors were calculated and supported by AM1 semi-empirical method calculation. The results show clearly that a fluorescent chemical sensor based on modified � - cyclodextrin detects quantitatively the presence of pesticides or herbicides and allow a direct analysis of these pollutants as a new method of detection with limits of the order of ppm for the whole of the analytes.

Contributions to the determination of histamine rate by measuring out the histamine–orthophthalaldehyde complex in the absorption and fluorescence☆

Histamine is an important compound from a physiological point of view, but it is toxic since the absorption of low amounts of histamine can cause abdominal pains accompanied with vomiting. Why we have developed a new method for histamine analysis in order to improve Lerke and Bell method. From the absorption spectra, we showed that the stoichiometry of the complex histamine-orthophthalaldehyde (OPA) is 1:1. From the emission spectra, it was observed that the complex fluorescence is inhibited in acidic medium. In alkaline medium, an exaltation of fluorescence was observed, but the complex histamine-OPA was unstable. Nevertheless, kinetic study showed that good linear correlations between the fluorescence maxima of the formed complex and the histamine concentration could be obtained in this alkaline medium.

Determination of phenylurea pesticides by direct laser photo-induced fluorescence

A direct Laser Photo-Induced Fluorescence (DL-PIF) method is developed for the determination of two phenylurea pesticides, namely fenuron and diflubenzuron. The DL-PIF method uses a tunable Nd:YAG-OPO Laser to obtain the photoproduct(s) and to simultaneously analyse their fluorescence in a short acquisition time on an intensified CCD camera. Compared to classical PIF methods, the use of a tunable laser improves the selectivity (by choosing the suitable excitation wavelength), increases the sensitivity (due to the high energy of the beam) and also reduces the time of analysis. The analytical performances of this method for the determination of both pesticides are satisfactory in comparison to other classical PIF methods published for the determination of phenylurea pesticides. The calibration curves were linear over one order of magnitude and the limits of detection were in the ng mL(-1) range. Satisfactory recoveries were obtained in the analysis of both pesticides in river and sea water spiked samples.

Quantitative treatment of the substituent effects on the electronic absorption spectra of indole derivatives

Abstract The electronic absorption spectra of twelve indoles with electron-donating groups have been determined at 298 K in several organic solvents. Hammett, Taft and Brown linear free energy relationships and Yukawa-Tsuno multiparametric correlations are obtained with the absorption maxima wavenumbers. The sensitivity of S 0 → S 1 ππ ∗ electronic transitions to various electronic effects is discussed.