Methoxsalen and suntanning; a blind study.
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We propose the 13C-detecting 1D DEPT long-range C-C relay to detect super long-range H-C connectivity via four bonds (1H-13C-X-X-13C, X represents 12C or heteronuclear). It is derived from the DEPT C-C relay which detects the H-C correlations via two bonds (1H-13C-13C) by setting the delays for J(CC) in the C-C relay sequence to the (LR)J(CC). This sequence gives correlation signals split by small (LR)J(CC), which seriously suffers from residual center signal. The unwanted signal is due to long-range C-H couplings ((LR)J(CH)). The expected relayed magnetization transfer 1J(CH) --> (LR)J(CC) occurs in the 1H-13C-X-(X)-13C isotopomer, whereas the unwanted signal of (LR)J(CH) comes from 1H-12C-(X)-13C isotopomers, whose population is 100 times larger than that of the 1H-13C-X-(X)-13C isotopomer. The large dispersive line of this unwanted center signal would be a fatal problem in the case of detecting small (LR)J(CC) couplings. This central signal could be removed by an insertion of BIRD pulse or X-filter. DEPT spectrum editing solved a signal overlapping problem and enabled accurate determination of particular (LR)J(CC) values. We demonstrate here the examples of structure determination using connectivity between 1H and 13C via four bonds, and the application of long-range C-C coupling constants to discrimination of stereochemical assignments.
Visnagin (4-methoxy-7-methyl-5H-furo [3,2-g][1]-benzopyran-5-one) is an active principle of the fruit of Ammi visnaga, a plant traditionally used in cardiovascular disorders. We have studied its vasodilator effects in rat vascular smooth muscle. The results demonstrated that visnagin inhibited the contractile responses induced in rat aortic rings by: (a) KCl or increases of extracellullar Ca2+ in KCl depolarized aortic rings, its effects being more potent against low (20 mM) than high (80 mM) KCl-induced contractions, (b) noradrenaline in Ca(2+)-containing solution and less effectively those in Ca(2+)-free solution and (c) phorbol 12-myristate 13-acetate (PMA) in a Ca(2+)-containing and with a lower potency in Ca(2+)-free medium. The relaxation induced by visnagin in aorta precontracted with noradrenaline was not affected by endothelium removal. Additionally, visnagin inhibited the spontaneous myogenic contractions of portal veins. The results showed that visnagin inhibited vascular smooth muscle contractility by acting at multiple sites. In the range of 10(-6) M to 5 x 10(-5) M visnagin appears to inhibit only the contractions mediated by Ca2+ entry through pathways with low sensitivity to classical Ca(2+)-entry blockers, i.e. agonist-, PMA- or mild depolarization-induced Ca2+ entry. Therefore, the vasodilator profile of visnagin, is not that of typical Ca(2+)-entry blockers which preferentially inhibit the contractions induced by strong depolarizations. At higher concentrations (> 5 x 10(-5) M) visnagin causes non-specific inhibition of vascular smooth muscle contractility.
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Many antiviral compounds obtained from plants are photosensitizers, i.e., their biological properties are dependent upon or augmented by light of specific wavelengths, commonly long wave ultraviolet, UVA. Three groups of chemically distinct plant photosensitizers have been investigated in some detail in regard to antiviral properties. These are (a) thiophenes and polyacetylenes; (b) furyl compounds; (c) certain alkaloids. Some of the thiophenes and their acetylenic derivatives possess extremely potent phototoxic activities toward membrane-containing viruses. These activities are markedly affected by the chemical structures of these compounds. Inactivated virus retains its integrity, however, and penetrates cells, but does not replicate. Their mechanism of action is believed to occur via singlet-oxygen damage to the membranes, although other targets cannot be ruled out. In contrast, the antiviral activities of plant furyl compounds (such as psoralens and furanochromones) appear to depend on UVA-mediated covalent adduct formation with the viral genomes. Some of the photoactive beta-carboline alkaloids also have impressive antiviral activities, especially against viruses with single-stranded genomes. These and other types of alkaloids appear to work by mechanisms that do not require covalent bonding to nucleic acids, and may also involve other target molecules as well. Some of these compounds have potent antiviral activities at concentrations well below cytotoxic levels, and accordingly should be tested in animal models.
A new, simple and rapid solid-phase extraction method for the determination of furanochromones and pyranocoumarins in Ammi visnaga L. fruits and pharmaceuticals by reversed-phase high-performance liquid chromatography (RP-HPLC) was developed. The isolation of compounds examined was carried out on octadecyl BakerBond SPE columns using various concentrations of methanol, acetonitrile and tetrahydrofuran in water. High and reproducible recoveries were obtained. To compare the results of quantitative analysis a preparative TLC procedure was also elaborated and carried out.