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691.
Polyaromatic thiophene compounds are found to occur concomitantly with numerous coal-derived products and shale oils and are suspected mutagens and/or carcinogens. The first synthesis of the two title compounds 9 and 16 has been achieved in five or four steps starting from 8,9-dihydroacenaphtho[1,2-b]benzo[d]thiophene (1) and 7-methoxynaphtho[1,2-b]thiophene (12), respectively. Compound 1 was converted to the cis-diol (11) (via treatment with OsO(4)/pyridine) or to trans-diol (3) [via Prevost reaction (PhCOOAg/I(2)) followed by hydrolysis] in 95-98% yield, respectively. Subsequent dehydration (PTS/benzene) of the diol followed by aromatization of the resulting ketone (5) produced the phenolic compound 6 in 97% yield. Oxidation of the phenol with phenyl iododiacetate followed by hydrolysis of the o-quinone monoketal 7 gave the o-quinone (8) in 86% yield. Stereoselective reduction of 8 with NaBH(4)/EtOH under oxygen afforded trans-10,11-dihydroxy-10,11-dihydroacenaphtho[1,2-b]benzo[d]thi oph ene(9) (orange yellow solid) in 55% yield. Compound 16 was obtained as a colorless solid, through the stereoselective reduction of the o-quinone 15 (with NaBH(4)), which in turn was prepared from 12 following the protocol of functional group transformation of methoxy --> phenol --> o-quinone monoketal --> o-quinone, as used in the previous case. The yields for all the steps are very good. The mutagenicity assay of compound 9 and 16 as well as their parent thiaarenes have been performed. The results showed that 9 may not be the proximate carcinogen of acenaphtho[1,2-b]benzo[d]thiophene, while it is likely that compound 16 is one of the possible proximate carcinogens for naphtho[1,2-b]thiophene. 相似文献
692.
Ultraviolet (UV)-mediated DNA damage in various tissues has been well documented. However, research on the damaging effect of UV irradiation on the DNA of corneal epithelium is scarce, even though this is of interest because the cornea is directly exposed to damaging solar (UV) radiation. In this study, we developed a corneal epithelium Comet assay model to assess the background DNA damage (as strand breaks) in cells retrieved from different layers of the porcine corneal epithelium, and to investigate the effect of UV irradiation on DNA damage in corneal epithelial cells. Results show that the background DNA strand breaks decreased significantly (P < 0.001) toward deeper layers of the epithelium. Exposure to the same intensity (0.216 J/cm2) of UVA, UVB and UVC caused a significant (P < 0.001) increase in DNA strand breaks of deeper-layer cells: mean +/- SD %DNA scores (10 gels per treatment, with 100 irradiated cells scored per gel) were 10.2% +/- 1.4% for UVA, 27.4% +/- 4.6% for UVB, and 14.7% +/- 1.8% for UVC compared with 4.2% +/- 0.5% for controls (ambient room light). This study has shown for the first time that the Comet assay for DNA strand breaks can be used successfully with corneal epithelial cells. This report will support future studies investigating environmental influences on corneal health and the assessment of possible protective strategies, and in applying DNA lesion-specific versions of the Comet assay in this corneal epithelial cell model. 相似文献
693.
Gandhi K. Kar Arun C. Karmakar Jayanta K. Ray 《Journal of heterocyclic chemistry》1991,28(4):999-1002
An improved synthesis of phenanthro[1,2-b]thiophene ( 6 ) from 1-chloro-3,4-dihydrophenanthrene-2-aldehyde ( 2 ) by condensation with thioglycolate followed by hydrolysis, decarboxylation and dehydrogenation is described. A new polycyclic thiophene derivative 14 has also been prepared from acenaphthothiophene ( 7 ) by Friedel-Craft's reaction with phthalic anhydride followed by lactonisation of the keto carboxylic acid 9 and then reduction and finally cyclisation of the resultant aldehyde 13 . 相似文献
694.
The off-the-shelf reagent PPN+Cl- and PPN-manganese carbonylates [PPN]+[Mn(CO)4L]- (L = CO, PPh3) are good catalysts for the coupling reactions of CO2 with neat epoxides without the use of organic solvents to afford cyclic carbonates. PPN salts with weak nucleophilic anions such as PPN+BF4- and PPN+OTf- are, however, inactive for the coupling reactions. 相似文献
695.
Protoporphyrin IX dimethyl ester (PME), a dimethyl esterification of protoporphyrin IX (PpIX), exhibits higher intracellular uptake into NPC/CNE2 cells, a poorly differentiated human nasopharyngeal carcinoma, than does PpIX. Phototoxicity studies reveal PME to be a more potent photosensitizer than is PpIX, at the early and late incubation time points. Correlating phototoxicity with subcellular localization indicates that PME is a more potent photosensitizer when its primary target of photodamage is mitochondria. Also, additional targeting of lysosome enhances phototoxicity. 相似文献
696.
Sorption of ammine complexes of Ni+2, Cu+2, Zn+2 and Cd+2 on hydrous Tin dioxide has been studied at different pH values. It has been found that qΔ and Kd values attain a maximum with increasing pH, beyond which a fall is observed. The selectivity quotients of the exchanger material towards competing pairs (Cu+2-Zn+2, Cu+2-Cd+2, Cu+2-Ni+2) of complex ions have been measured as a function of the concentration of the external solution. The selectivity of the exchanger material towards the preferred ion decreased with increase in the concentration of the competing ions in the external solution. The selectivity and the sorption values (qδ) follow the same order. 相似文献
697.
Santi R. Palit Indrajit Kar 《Journal of polymer science. Part A, Polymer chemistry》1967,5(10):2629-2636
Solomon and Ciuta's equation has been deduced from first principles and has been shown to be merely an algebraic consequence of the definition of intrinsic viscosity. Secondly, a consequence of this equation that [η]c should be linear with \documentclass{article}\pagestyle{empty}\begin{document}$\sqrt {2\eta {\rm sp} - 2\ln \eta {\rm rel}}$\end{document} with unit slope, is found to be fairly accurate when examined against literature and our own data, and so this equation is commended not only for single-point determination of [η] but also for representing viscosity variation with concentration up to ηsp < 0.60. Thirdly, higher-order approximations are found to be less suitable. Other consequences of Solomon and Ciuta's equation are discussed. 相似文献
698.
699.
We consider a model correlated percolative system on a 2D square lattice with a finite electric field applied accross its two opposite sides. We study the shape of the clusters formed with the addition of a new kind of bond (we call them tunneling bonds) which respond only above a finite threshold voltage. As expected, the clusters do have an overall elongated shape in the-direction of the applied field. Intuitively, one expects the elongation (with the aspect ratio >1) to increased indefinitely with the field. But, in a previous study, we found the model to belong to the same universality clas in the limits of a zero and an infinite electric field. We explain this behavior by studying the change in these elongated shapes as a function of the applied voltage in finite size samples and find that actually the amount of elongation takes on a maximum value at a size (L)-dependent finite voltageV
m
(L) and that asV thje overall deviation from isotropy in the field direction tends to zero (i.e., aspect ratio1) again. 相似文献
700.