Studies in tertiary amine oxides. Part V—carbon-13 nuclear magnetic resonance spectra of some N-aryl tertiary amines,the corresponding N-oxides and the meisenheimer rearrangement products

The carbon-13 NMR spectra of some N-(2- or 4-nitrophenyl) tertiary amines and their corresponding N-oxides have been analysed. These N-oxides undergo thermal rearrangement to O-arylhydroxylamines, for which the ¹³C NMR spectral assignments were also carried out. The N-oxidation effect on the aromatic and aliphatic fragments is calculated.     

Isolation of onosmins A and B, lipoxygenase inhibitors from Onosma hispida

Onosmins A (1) and B (2), lipoxygenase inhibitors, have been isolated from Onosma hispida. Their structures were established as 2-[(4-methylbenzyl)amino]benzoic acid (1) and methyl 2-[(4-methylbenzyl)amino]benzoate (2) through spectroscopic studies, including 2D-NMR. The known compounds apigenin (3), 6,4'-dimethoxy-3,5,7-trihydroxyflavone (4), 6,7-dimethoxy-3,5,4'-trihydroxyflavone (5) and apigenin 7-O-beta-D-glucoside (6) are also reported for the first time from this species. Compounds (1) and (2) inhibited lipoxygenase (LOX, EC 1.13.11.12) enzyme in a concentration-dependent fashion with IC50 values of 24.0 and 36.2 microM, respectively. Lineweaver-Burk as well as Dixon plots and their secondary replots indicated that the nature of inhibition was purely a non-competitive type, with K(i) values 22.0 microM and 31.1, respectively.     

Lipoxygenase inhibiting constituents from Indigofera hetrantha

A lignan and two acylphloroglucinols have been isolated from the ethyl acetate soluble fraction of the whole plant of Indigofera hetrantha. Their structures have been assigned on the basis of spectral analysis including 1D and 2D NMR techniques. Compounds 1-3 displayed promising inhibitory potential against enzyme lipoxygenase in concentration-dependent manner.     

Tyrosinase-inhibitory long-chain esters from Amberboa ramosa

Long-chain esters 1 and 2 have been isolated from the chloroform-soluble fraction of Amberboa ramosa and their structures assigned to be methyl 2beta(2S)-hydroxyl-7(E)-tritriacontenoate (1) and methyl 2beta(2S)-O-beta-D-galactopyranosyl-7(E)-tetratriacontenoate (2). In addition, tricontane (3) and apigenin (4) are also reported for the first time from this species. The structures were assigned on the basis of 1D and 2D NMR techniques. Compounds 1 and 2 showed strong to moderate inhibitory activity against tyrosinase.     

Solvent and substituent effects on spectroscopical changes of some diazoaminobenzene derivatives

A series of diazoaminobenzene derivatives (seven) in which the substituents have a wide range of electronic characters are set out to understand the involvement of the substituent identity in controlling the changes in their electronic absorption spectra. The interactions between the diazoamino group and the different groups account for some spectral shifts. The UV-vis spectrum of each compound is measured in several solvents with wide variations of solvent polarity parameters to examine the role of the chemistry of the solvent in these spectroscopical changes. The electronic transitions are assigned and the solvent induced spectral shifts are analyzed in relation to the different solute-solvent interaction mechanisms using computational chemistry. The regression analysis is applied for correlating the different parameters. The results help to assign the solute-solvent interactions and the solvatochromic potential of the investigated compounds. It is concluded that the electronic character of the substituent and the chemical nature of the solvent are the major factors for the observed solvatochromism.     

Transfer of radioactivity from soil to vegetation in Rechna Doab, Pakistan

In Rechna Doab, samples of the most common vegetation, perennial grass Desmostachya bipinnata (dab), were collected along with soil samples from 29 sites. Natural radioactivity of 22?Ra, 232Th/22?Ac and ??K was measured by using high purity germanium-based gamma ray spectrometer. Activity concentration levels of 22?Ra, 232Th/22?Ac and ??K in soil were found to be 46.8 ± 6.2 (36.0-57.6), 61.4 ± 5.9 (48.2-73.2) and 644.8 ± 73.9 (537.7-868.4) Bq kg?1 (dry mass), respectively, and those in vegetation were 2.74 ± 1.70 (1.00-6.39), 2.24 ± 0.59 (1.56-2.61) and 172.72±113.37 (53.14-469.24) Bq kg?1 (dry mass), respectively. The measured values of the activity concentration in vegetation are comparable with some other international data. Calculated soil to vegetation transfer factors of 22?Ra, 22?Ac and ??K were 0.06 ± 0.03 (0.02-0.14), 0.04 ± 0.01 (0.03-0.04) and 0.26 ± 0.16 (0.09-0.69). The mean outdoor absorbed dose rate in air for the area under study was determined as 8.22 nGy h?1 and the mean indoor absorbed dose rate in air was 11.52 nGy h?1. The total annual effective dose to the general public from the vegetation was found to be (0.02-0.16) mSv, which is below the recommended limit value of 1 mSv y?1 for the general public. The dab vegetation under study was found to be radiologically safe for the population and environment.     

Cucurbitacin glucosides from Citrullus colocynthis

A new cucurbitacin glucoside 2-O-beta-D-glucopyranosyl-16alpha-20R-dihydroxy-cucurbita-1,5,23E,25(26)-tetraen-3,11,22-trione (1) has been isolated from the methanolic extract of the fruits of Citrulluscolocynthis. The structure has been assigned on the basis of spectral analysis including 1D and 2D NMR techniques. In addition 2-O-beta-D-glucopyranosyl-cucurbitacin B (arvenin I) (2) and 2,25-di-O-beta-D-glucopyranosyl-cucurbitacin L (3) are reported for the first time from this species.     

Early excited state dynamics of 6-styryl-substituted pyrylium salts exhibiting dual fluorescence

A series of 6-styryl-2,4-diphenylpyrylium salts exhibiting dual fluorescence has been investigated by fluorescence up-conversion in conjunction with quantum chemical calculations. The short-wavelength emission is due to an excited state localized on the pyrylium fragment and the long-wavelength emission arises from a charge-transfer state delocalized over the whole molecule. The two fluorescing states do not exhibit a precursor-successor relationship. The rise time of the short-wavelength fluorescence is smaller than 200 fs, and that of the long-wavelength emission depends on the electron-donating property of the styryl group substituent. The rise is almost prompt with the weaker donors but is slower, wavelength and viscosity dependent with the strongest electron-donating group. A model involving a S(2)/S(1) conical intersection is proposed to account for these observations.