Optogalvanic spectra of calcium in the 6090–6760 Å region

Optogalvanic spectra of some 30 transitions of calcium originating from the ground state as well as from several excited states (4s4p ^1,3P, 4s3d ^1,3D, 4s5p ³P, 3d4p ³D, ³F) have been investigated using laser-irradiation of a low-current glow discharge in a thermionic diode. The influence of various experimental parameters such as bias field, oven temperature and buffer gas pressure on the spectra are reported. Seven previously unreported transitions are recorded including four forbidden transitions which violate the J selection rules. An interesting anomaly observed in the non-statistical population of the 4s3d ³D_3,2,1 multiplet is discussed where the populations of ³D₃:³D₂:³D₁ are in the ratio of 94:5:1. A possible explanation is based on avoided crossing between potential energy curves of the Ca-Ar molecule.     

A new route to trinuclear carbocyanines

Amides or vinylogous amides react with tosyl chloride-pyridine to form activated intermediates which condense with Fischer's base or their vinylogs to give carbocyanine structures. Under the same conditions formylated Fischer's base reacts with vinylogous Fischer's bases to give trinuclear carbocyanines in good yields. Their structure and the limitations of this route are discussed.     

Quantitative determination of usnic acid in Usnea lichen and its products by reversed-phase liquid chromatography with photodiode array detector

Usnic acid, a lichen substance, has a wide range of pharmaceutical applications, including antibiotic, antimycotic, antifeedant, antitubercular, antitumor, and analgesic activities. Some products containing usnic acid are marketed as weight control supplements; however, hepatotoxicity and acute liver failures were reported as severe side effects. The usnic acid content present in the plant materials and market products was analyzed by reversed-phase high-pressure liquid chromatography with a photodiode array detector at 233 nm. A Waters XTerra RP18 (150 x 4.6 mm; 5 microm particle size) column was the stationary phase; mobile phase was aqueous 0.1% acetic acid and acetonitrile gradient at flow rate of 1.0 mL/min. The temperature was held constant at 30 degrees C. The retention time of usnic acid was approximately 13.3 min. Acetone extraction of the samples took place with sonication. The precision of the method was confirmed by a standard deviation below 3.0% (n=3) and usnic acid recovery was 99.0%. Limit of detection was 0.4 microg/mL and the response was linear from 1.4 to 570.0 microg/mL with a correlation coefficient (R2) of 0.9991. The content of usnic acid in 4 raw materials and 22 finished products was analyzed.     

Fused pyrazolopyrimidines. I. Pyrazolo[4,3-e]-v-triazolo[1,5-a]pyrimidine. A new heterocyclic system

5-Azido-4-cyano-1-phenylpyrazole reacts with benzylcyanide in the presence of sodium methoxide to give the title ring system.     

Steric guided change of electron transfer mechanism in benzene

In fluorescence quenching study via electron transfer (ET), the quenching rate constant (k(q)) values generally decrease with lowering of quencher concentration, since smaller concentration of quencher always leads to a red shift in the donor-acceptor (D-A) distance in ET [M. Tachiya, S. Murata, J. Phys. Chem. 96 (1992) 8441; S. Murata, M. Tachiya, J. Phys. Chem. 100 (1996) 4064; L. Burel, M. Mastafavi, S. Murata, M. Tachiya, J. Phys. Chem. A 103 (1999) 5882]. However, while doing a comparative study with different carbazole (CZ) derivatives-1,4-dicyanobenzene (DCB) systems in benzene (BZ), we observed a deviation from that normal behaviour. It was found that for all of them with lower quencher (DCB) concentration, k(q) values actually increase instead of the expected reduction. Exceptionally, for simple CZ (C12H9N) with decrease in concentration of DCB, k(q) values can even reach the order of energy transfer (10(11) s(-1)). Interestingly, it is not observed when toluene (TL) or xylene (XY) is used as solvent. To explain this unique observation, a sandwich type of molecular structure is predicted, where BZ sliding in between CZ and DCB brings them closer enough, imparting more through bond character to CZ-DCB interaction and hence a higher rate of ET (k(q)) is observed [L. Burel, M. Mastafavi, S. Murata, M. Tachiya, J. Phys. Chem. A. 103 (1999) 5882].     

Enantioselective catalytic epoxidation of nonfunctionalized prochiral olefins by dissymmetric chiral Schiff base complexes of Mn(III) and Ru(III) metal ions II

A series of new dissymmetric chiral Schiff base complexes has been obtained by a systematic condensation of (1S,2S)(+)-diaminocyclohexane and 3-acetyl-4-hydroxy-6-methyl-2-pyrone with salicylaldehyde, 5-chloro-, 5-methoxy-and 5-nitrosalicylaldehyde and by subsequent metallation with manganese and ruthenium. The characterization of the complexes 1–8 was accomplished by physico chemical studies viz. microanalysis, IR-, UV/VIS-, and CD spectral studies, optical rotation, molar conductance measurements and cyclic voltammetry. Enantioselective epoxidation of non functionalised olefins, viz. cis-stilbene, trans-3-nonene and trans-4-octene with iodosyl benzene as oxidant was demonstrated in the presence of catalytic amounts of chiral Mn(III) and Ru(III) dissymmetric Schiff base complexes. Good optical yields of epoxides were obtained for the catalyst 4 with the substrates trans-3-nonene and cis-stilbene.     

Thin-Layer Chromatographic Separation of Cadaverine and Ornithine,and Spectrophotometric Quantification

JPC – Journal of Planar Chromatography – Modern TLC -