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 (-contribution) and the vector sum of the -bond and group moments (-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 the-electron densities resulting in a more polar excited state. There is a reasonably good agreement between the calculated and the experimental dipole moments.Presented, in part, at the 2nd International Conference on Solar Energy Storage and Applied Photochemistry, Cairo, Egypt, January 6–11, 1993. For a preliminary communication, see Ref. 1.     

A new 3-arylcoumarin from the roots of an Egyptian collection of Lotus polyphyllos

Further investigation of different fractions from Lotus polyphyllos Clarke roots resulted in the isolation of the new 3-arylcoumarin derivative; 4',6'-dihydroxy-7, 2'-dimethoxy-3-arylcoumarin (5). In addition, the known compounds beta-sitosterol, 1-hexacosanol (1), n-tetracosyl p-coumarate (2), 4'-O-methylderrone (4), and quercetin (6) were identified. The structures were determined from spectroscopic data including 1D- and 2D-NMR experiments.     

Excited state intramolecular proton transfer in 2-(2'-arylsulfonamidophenyl)benzimidazole derivatives: insights into the origin of donor substituent-induced emission energy shifts

Donor-substituted 2-(2'-arylsulfonamidophenyl)benzimidazoles undergo efficient excited-state intramolecular proton transfer (ESIPT) upon photoexcitation. The tautomer emission energy depends strongly on the substituent attachment position on the fluorophore pi-system. While substitution with a donor group in the para-position relative to the sulfonamide moiety yields an emission energy that is red-shifted relative to the unsubstituted fluorophore, fluorescence of the meta-substituted derivative appears blue-shifted. To elucidate the origin of the surprisingly divergent emission shifts, we performed detailed photophysical and quantum chemical studies with a series of methoxy- and pyrrole-substituted derivatives. The nature and contribution of solvent-solute interactions on the emission properties were analyzed on the basis of solvatochromic shift data using Onsager's reaction field model, Reichardt's empirical solvent polarity scale ET(30), as well as Kamlet-Abboud-Taft's empirical solvent index. The studies revealed that all ESIPT tautomers emit from a moderately polarized excited-state whose dipole moment is not strongly influenced by the donor-attachment position. Furthermore, the negative solvatochromic shift behavior was most pronounced in protic solvents presumably due to specific hydrogen-bonding interactions. The extrapolated gas-phase emission energies correlated qualitatively well with the trends in Stokes shifts, suggesting that solute-solvent interactions do not play a significant role in explaining the divergent emission energy shifts. Detailed quantum chemical calculations not only confirmed the moderately polarized nature of the ESIPT tautomers but also provided a rational for the observed emission shifts based on the differential change in the HOMO and LUMO energies. The results gained from this study should provide guidelines for tuning the emission properties of this class of ESIPT fluorophores with potential applications in analytical chemistry, biochemistry, or materials science.     

Chemical composition,antimicrobial and insecticidal activities of the essential oils of Conyza linifolia and Chenopodium ambrosioides

Two essential oil-containing plants growing wildly in Egypt: Conyza linifolia (Willd.) Täckh. (Asteraceae) and Chenopodium ambrosioides L. (Chenopodiaceae) were subjected to essential oil analysis and biological investigation. The essential oils from both plants were prepared by hydrodistillation, and GC/MS was employed for volatiles profiling. This study is the first to perform GC/MS analysis of C. linifolia essential oil growing in Egypt. C. linifolia essential oil contained mainly sesquiterpenes, while that of C. ambrosioides was rich in monoterpenes. Ascaridole, previously identified as the major component of the latter, was found at much lower levels. In addition, the oils were investigated for their antimicrobial activity against two Gram positive and two Gram negative bacteria, and one fungus. The insecticidal activities of both oils, including mosquitocidal and pesticidal potentials, were also evaluated. The results of biological activities encourage further investigation of the two oils as antimicrobial and insecticidal agents of natural origin.     

Parameters affecting carbofuran photocatalytic degradation in water using ZnO nanoparticles

Carbofuran photodegradation in water using zinc oxide nanoparticles as a catalyst was examined as well as some parameters influencing its percentage degradation rate such as zinc oxide load, initial concentration of carbofuran, the temperature of the reaction, the initial pH of the solution, and doping of zinc oxide nanoparticles with 5% (w:w) silver. Zinc oxide and Ag-doped zinc oxide nanoparticles were produced using solvothermal and photoreduction methods, respectively, and silver doping effects on the structural, optical, and photocatalytic properties of zinc oxide nanoparticles were investigated using XRD, UV-VIS spectrophotometer, TEM, SEM, SEM/EDX, and FTIR. The average diameter of the synthesized samples was 26.6, 30.55 nm for undoped zinc oxide and Ag-doped zinc oxide, respectively. Zinc oxide doping with silver did not change the shape of the zinc oxide crystal, but decreased the reflection in the visible region, as well as the energy of the bandgap, and increased the zinc oxide photocatalytic activity.