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Conclusions The decomposition of the complex obtained in the reaction of pivaloyl tetrafluoroborate with norcarane and its 1-methyl and 1-phenyl derivatives by water gives 1-hydroxy-3-pivaloyl derivatives of cyclohexanes and the corresponding unsaturated ketones. The hydride decomposition of the same complex leads to derivatives of 6-oxabicyclo[3.2.1]octane.For preliminary report see [1].Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2512–2518, November, 1976. 相似文献
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Melanin offers protection against induction of cyclobutane pyrimidine dimers and 6-4 photoproducts by UVB in cultured human melanocytes 总被引:3,自引:0,他引:3
Smit NP Vink AA Kolb RM Steenwinkel MJ van den Berg PT van Nieuwpoort F Roza L Pavel S 《Photochemistry and photobiology》2001,74(3):424-430
The goal of this investigation was to correlate the melanin content in human pigmentary cells with the generation of UVB-induced photoproducts and to examine the relationship between the melanin content and the removal of the photoproducts. Cultured melanocytes from light-skinned individuals synthesized less melanin and produced more cyclobutane pyrimidine dimers and 6-4 photoproducts upon UVB exposure than did melanocytes from black skin. Tyrosine-stimulated melanogenesis provided protection against DNA damage in both cell types. In another set of pigmented cell lines a ratio between eumelanin and pheomelanin was determined. The assessment of association between DNA damage induction and the quantity and quality of melanin revealed that eumelanin concentration correlated better with DNA protection than pheomelanin. Skin type-I and skin type-VI melanocytes, congenital nevus (CN)-derived cells and skin type-II melanocytes from a multiple-melanoma patient were grown in media with low or high L-tyrosine concentration. The cells were irradiated with 200 J/m2 UVB, and the levels of the photoproducts were determined immediately and after 6 and 24 h. Once again the induction of the photoproducts was mitigated by increased melanogenesis, and it was inversely correlated with the skin type. No significant differences were found for the removal of photoproducts in the cultures of skin types I and VI and CN cells. No indications of a delay in the removal of photoproducts in the melanocytes from the multiple-melanoma patient were found either. 相似文献
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1. | From MNDO quantum chemical calculations, opening of the episulfonium ion ring by neutral nucleophiles X (X=NH3 and HCN) and related SN2 reactions of protonated methylthiol (PMT) with X proceed through formation of pre-reaction complexes in which X is coordinated either at the reacting C atom or (only in opening of episulfonium ion rings) at the center of the C-C bond. |
2. | In their electronic structure, the transition states for the reactions are reminiscent of a carbocation simultaneously reacting with the attacking and the leaving nucleophilic fragments (X S). |
3. | Opening of episulfonium ion rings proceeds slightly more easily (Ea 10–12 kcal/mole) than substitution in PMT (Ea 22–25 kcal/mole). The ease of ring opening for episulfonium ions is due to the large exothermicity of the reaction and the lower internal activation barrier compared with SN2 reactions in PMT. |
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A two-step synthesis was proposed for the tetracyclic triquinane bis-enone from two monocyclic precursors. The bis-enone obtained is a structural fragment of retigeranic acid.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1908–1910, August, 1990. 相似文献