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1.
In proportion to the environmental pollution problems caused by organotin compounds, the genotoxicities of tin compounds in the environments have become of interest so as to estimate their safety in recent years. In this work, isolated λ-DNA (double-strand DNA) was incubated with inorganic tin(II) and tin(IV) and five organotin compounds [n-butyltin trichloride, di(n-butyltin) dichloride, methyltin trichloride, dimethyltin dichloride and trimethyltin chloride] in reaction systems both with and without hydrogen peroxide (H2O2) content. The tin compounds tested in this study did not induce DNA breakage in the absence of hydrogen peroxide. Divalent inorganic tin (SnCl2) and tetravalent inorganic tin (SnCl4) caused DNA breakage in the presence of hydrogen peroxide (10 mM), and the DNA damage activity of inorganic tin was much more potent in divalent inorganic tin (SnCl2) than in tetravalent inorganic tin (SnCl4). Divalent inorganic tin (SnCl2) induced DNA breakage in a concentration-dependent fashion at concentrations greater than 0.1 mM of SnCl2 in the presence of hydrogen peroxide (10 mM). DNA breakage was not caused by n-butyltin compounds and methyltin compounds either in the presence or in the absence of hydrogen peroxide. 相似文献
2.
S Ozaki T Akiyama T Morita M Kumegawa T Nagase N Uehara A Hoshi 《Chemical & pharmaceutical bulletin》1990,38(11):3164-3166
Various kinds of 5'-O-unsaturated acyl 5-fluorouridines were synthesized to obtain 5-fluorouridine derivatives with low toxicity and high antitumor activity. Antitumor activity of the compounds against L-1210 leukemia in mice was examined, and the 5'-O-4-pentenoyl derivative showed the highest antitumor activity. 相似文献
3.
Relative concentrations of nine isomers of Ca at C82 derived from the C82 isolated-pentagon-rule satisfying cages are computed in a wide temperature interval. The computations are based on the Gibbs energy constructed from partition functions supplied with molecular parameters from density functional theory calculations. Five structures show significant populations at higher temperatures: C2v > Cs > C2 > C3v > Cs. The computed relative stabilities agree well with available observations. 相似文献
4.
The intermolecular interaction energy for reacting systems in singlet, triplet and doublet states was partitioned by the perturbation expansion method into the chemically meaningful five interaction terms: the Coulomb, exchange-repulsion, induction, dispersion, and charge-transfer energies. In the local ZDO approximation, these energy terms were evaluated for the dimerization of methylenes (1,3CH2), the additions of carbenes (1,3CH2 and1,3CF2) as well as amino radicals (2NH2 and2NF2) toward ethylene, and the hydrogen abstractions by methylenes (1,3CH2), nitrene (3NH), and hydroxyl radical (2OH) from methane. It has been found that the reaction path is much influenced by the spinmultiplicity, and that the charge-transfer and exchange-repulsion terms play a dominant role in determining the course of reactions. 相似文献
5.
The electrical properties of polycrystalline lithium chloroboracite, Li4B7O12Cl, prepared by the sol-gel method were investigated in connection with their structure. Li4B7O12Cl pellets were prepared with different amounts of hydrochloric acid or ammonium chloride. The kind and amount of the chlorine source affected the formation of by-products (Li2B4O7, LiCl, a glass phase) and the morphology of the Li4B7O12Cl pellets. Thus their conductivity, which is dominated by grain boundary response owing to the high porosity of the materials, was also affected. The formation of Li2B4O7 as a by-product led to a higher activation energy and lower conductivity. In those pellets in which Li2B4O7 did form, an increase of the amount of glass phase led to higher conductivities. 相似文献
6.
Fujii H Hirano N Uchiro H Kawamura K Nagase H 《Chemical & pharmaceutical bulletin》2004,52(6):747-750
7beta-Carbamoyl-4,5alpha-epoxymorphinans 5 were stereoselectively synthesized from the 7alpha-carboxylate intermediate 3 in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and amines under reflux conditions in mesitylene via a novel and reactive gamma-lactone 7. These were the first examples of the stereoselective syntheses of 7beta-substituted 4,5alpha-epoxymorphinans. The mechanism of the reaction process was elucidated as follows: 1) epimerization of 7alpha-carboxylate 3, 2) intramolecular lactonization of 7beta-carboxylate 6, and 3) aminolysis of the resultant gamma-lactone 7. The aminolysis of the isolated reactive gamma-lactone 7 with allylamine and the alcoholysis with MeOH in the presence of NaBH(4) proceeded at room temperature. The gamma-lactone 7 can be a useful intermediate for the preparation of 7beta-substituted 4,5alpha-epoxymorphinans that would be potent selective delta opioid receptor ligands. The stereoselective syntheses of the 7alpha-carbamoyl-4,5alpha-epoxymorphinans 9 from 7alpha-carboxylate 3 via 7alpha-carboxylic acid were also successful. 相似文献
7.
To provide theoretical insight into the structures and properties of Sc3N@C80, which has been isolated in high yield and purity as a new stable endohedral metallofullerene, density functional calculations are carried out for the Sc3?nLanN@C80 (n=0–3) series. Because of electron transfer from Sc3N to C80, the electronic structure of Sc3N@C80 is formally described as (Sc3N)6+C$_{80}^{6-}$. The encapsulated Sc3N cluster takes a planar structure with long Sc–Sc distances and is highly stabilized inside the Ih cage of C80, which rotates rapidly. As the number of La atoms increases, the Sc3?nLanN cluster is forced to maintain a pyramidal structure in Sc3?nLanN@C80. In addition, the C80 cage takes an open‐shell electronic structure due to an increase in the number of electrons transferring from Sc3?nLanN. These make the endohedral structure less stable and more reactive. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1353–1358, 2001 相似文献
8.
Cao B Wakahara T Tsuchiya T Kondo M Maeda Y Aminur Rahman GM Akasaka T Kobayashi K Nagase S Yamamoto K 《Journal of the American Chemical Society》2004,126(30):9164-9165
A new metallofullerene, La2@C78, has been synthesized by DC arc discharge method, isolated by high-performance liquid chromatography, and characterized by laser desorption time-of-flight mass spectrometry, UV-vis-NIR absorption, differential pulse voltammetry, 13C NMR spectroscopy, and theoretical calculations. The La2@C78/CS2 solution is dark violet and presents several characteristic absorption features at 647, 561, 533, and 386 nm, with an onset around 1000 nm. With respect to empty D3-C78, the capability of La2@C78 as an electron acceptor or donor is stronger. Addition of 1,1,2,2-tetrakis(2,4,6-trimethylphenyl)-1,2-disirane to La2@C78 photochemically, as well as thermally, affords bis- and mono-adducts. Theoretical studies and 13C NMR spectroscopic analysis of La2@C78 indicate that it possesses a D3h-C78 cage (78:5). 相似文献
9.
Certain amides and thioamides can easily be methylated with diazomethane in the presence of silica gel. 相似文献
10.
Masao Ikeda Takashi Nakamura Yu Nagase Koji Ikeda Yoshiro Sekine 《Journal of polymer science. Part A, Polymer chemistry》1981,19(10):2595-2607
For the purpose of studying the mechanism of thermal degradation of poly[(tetramethyl-p-silphenylene) Siloxane] (poly TMPS) a series of polymers with silphenylene and siloxane bonds in the main chain were prepared and subjected to thermogravimetry (TG) and pyrolysis study. Analyses of products from poly TMPS degradation (in vacuum at a constant temperature) by gas chromatography (GC), infrared (IR), nuclear magnetic resonance (NMR) spectroscopy, and gas chromatography-mass spectrometry (GC–MS) revealed that degradation occurs at the silphenylene bonds. The TG curves obtained in He for heating rates of 1,2,2.5,7.5, and 10°C/min were analyzed by the Ozawa method; activation energies of 39 ± 1 and 45 ± 2 kcal/mol were obtained respectively for the initial cleavage of the methyl side group and the later-stage scission of the main-chain silphenylene bond which leads to a major weight loss. The results agree with those obtained for other structurally similar polymers. 相似文献