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311.
Under simulated environmental (atmospheric) conditions, chloropicrin vapor was readily converted in light to phosgene, which remained stable, and nitrosyl chloride which was subsequently photolyzed to nitric oxide and chlorine; a portion of the nitric oxide was oxidized to nitrogen dioxide and dinitrogen tetroxide. The unexpected dependence of the reaction upon oxygen, the initial photoproducts, and the incorporation of 18O when the photolysis occurred in the presence of 18O2 suggest an intramolecular rearrangement involving a trioxazole N-oxide. 相似文献
312.
The procedure presented for gas-liquid chromatographic analysis of alpha-keto acids is relatively simple, requiring only a few steps for the formation of derivatives suitable for measurement. The recoveries of the branched-chain alpha-keto acids varied from 92.7% to 106.7%, being sufficiently good especially when smaller amounts of the alpha-keto acids were added to serum. In addition, the coefficients of variation are satisfactorily small, also for biological samples. The measured values of branched-chain alpha-keto acids correspond well with those presented earlier by different methods. There exists a slight but insignificant difference between women and men, the values being lower in sera of women for the three branched-chain alpha-keto acids studied. 相似文献
313.
Regulation of copper/zinc and manganese superoxide dismutase by UVB irradiation, oxidative stress and cytokines 总被引:3,自引:0,他引:3
314.
The structure, energetics, and vibrational properties of complexes formed between H2S and CO have been investigated by matrix isolation FTIR spectroscopy and ab initio molecular orbital theory. Two stable computational minima were found representing nearly linear hydrogen bonds between the subunits. The H2S---CO and H2S---OC species were calculated to be bound by 5.22 and 1.54 kJ mol−1, respectively. The computational results were reproduced by experimental assignments for the carbon attached complex. The stretching vibrations of the complex subunits were found to be similarly perturbed upon complexation both experimentally and computationally. 相似文献
315.
Kontturi M Laurila E Mattsson R Peräniemi S Vepsäläinen JJ Ahlgrén M 《Inorganic chemistry》2005,44(7):2400-2406
Four new zinc and cadmium bisphosphonates [{NaZn(Cl2CP2O6H)(H2O)5}]n (1), [{Cd2(Cl2CP2O6)(H2O)4}.H2O]n (2), [{Zn(Cl2CP2O6Pri2)(H2O)3}.H2O]n (3), and [{Cd2(Cl2CP2O6Pri2)2(MeOH)2(H2O)2}.H2O]2 (4) have been prepared and their crystal structures determined by single-crystal X-ray diffractometry. Two bisphosphonate ligands were used: clodronate, (dichloromethylene)bis(phosphonate) and its symmetrical P,P'-diisopropyl ester derivative. The structure of the Zn complex 1 is three-dimensional, consisting of one-dimensional Zn-clodronate chains connected to the three-dimensional network by Na+ ions. The structure of Cd complex 2 consists of double layers, and a unique bond was found between the Cd2+ cation and a Cl atom of clodronate. Zn complex 3 consists of one-dimensional chains, but the binding of the bisphosphonate ligands is unique: in 3 the bisphosphonate ligand is only bidentate. Compound 4 is a tetramer, and hydrogen bonds hold the tetramers together, forming a layered structure. 相似文献
316.
Colacio E Kivekäs R Lloret F Sunberg M Suarez-Varela J Bardají M Laguna A 《Inorganic chemistry》2002,41(20):5141-5149
A family of cyano-bridged copper(II)-copper(I) mixed-valence polymers containing diamine ligands of formula [Cu(pn)(2)][Cu(2)(CN)(4)] (1, pn = 1,2-propanediamine), [Cu(2)(CN)(3)(dmen)] (2, dmen = N,N-dimethylethylenediamine), and [Cu(3)(CN)(4)(tmen)] (3, tmen = N,N,N',N'-tetramethylethylenediamine) have been prepared with the aim of analyzing how their architecture may be affected by steric constraints imposed by the diamine ligands. In the absence of diamine and with use of the voluminous NEt(4)(+) cation, the copper(I) polymer [NEt(4)][Cu(2)(CN)(3)] (4) forms. The structure of 1 consists of a three-dimensional diamond-related anionic framework host, [Cu(2)(CN)(4)](2-), and enclathrated [Cu(pn)(2)](2+) cations. The structure of 2 is made of neutral corrugated sheets constructed from fused 18-member nonplanar rings, which contain three equivalent copper(I) and three equivalent copper(II) centers bridged by cyanide groups in an alternative form. The 3D structure of 3 consists of interconnected stair-like double chains built from fused 18-member rings, which adopt a chairlike conformation. Each ring is constructed from two distorted trigonal planar Cu(I) centers, two bent seemingly two-coordinated Cu(I) centers, and two pentacoordinated Cu(II) atoms. The structure 4 is made of planar anionic layers [Cu(2)(CN)(3)](n)(n-) lying on mirror planes and NEt(4)(+) cations intercalated between the anionic layers. From the X-ray structural results and calculations based upon DFT theory some conclusions are drawn on the structure-steric factors correlation in these compounds. Compound 1 exhibits very weak luminescence at 77 K with a maximum in the emission spectrum at 520 nm, whereas compound 4 shows an intense luminescence at room temperature with a maximum in the emission spectrum at 371 nm. Polymers 2 and 3 exhibit weak antiferromagnetic magnetic exchange interactions with J = -0.065(3) and -2.739(5) cm(-1), respectively. This behavior have been justified on the basis of the sum of two contributions: one arising from the pure ground-state configuration and the other one from the charge-transfer configuration Cu(I)-CN-Cu(II)-CN-Cu(II) that mixes with the ground-state configuration. 相似文献
317.
Conjoint analysis, a preference measurement method typical in marketing research, has gradually expanded to other disciplines. Choice-based conjoint analysis (CBC) is currently the most popular type. Very few alternative estimation approaches have been suggested since the introduction of the Hierarchical Bayes (HB) method for estimating CBC utility functions. Studies that compare the performance of more than one of the proposed approaches and the HB are almost non- existing. We compare the performance of four published optimization-based procedures and additionally we introduce a new one called CP. The CP is an estimation approach based on convex penalty minimization. In comparison with HB as the benchmark we use eight field data sets. We base the performance comparisons on holdout validation, i.e. predictive performance. Among the optimization based procedures CP performs best. We run simulations to compare the extent to which CP and HB can recover the true utilities. With the field data on the average, the CP and HB results are equally good. However, depending on the problem characteristics, one may perform better than the other. In terms of average performance, the other four methods were inferior to CP and HB. 相似文献
318.
Samuli Siitonen Juha Pietarinen Pasi Laakkonen Konstantins Jefimovs Markku Kuittinen Teemu Alajoki Kari Mönkkönen Esko J. Pääkkönen Ari Tervonen 《Optical Review》2007,14(5):304-309
Planar light guide plate with one in-coupling and N out-coupling surface relief gratings is designed to perform as optical backplane broadcasting system for board-to-board connections.
The performance of the element is analyzed theoretically with rigorous electromagnetic theory and results are confirmed experimentally.
In addition, optical backplane elements have been replicated using conventional injection molding and UV-replication techniques. 相似文献
319.
Let G be a group with a dihedral subgroup H of order 2pn, where p is an odd prime. We show that if there exist H-connected transversals in G, then G is a solvable group. We apply this result to the loop theory and show that if the inner mapping group of a finite loop Q is dihedral of order 2pn, then Q is a solvable loop.1991 Mathematics Subject Classification: 20D10, 20N05 相似文献
320.
A Ti(Oi-Pr)4-mediated kinetic spiroketalization reaction has been developed for the stereocontrolled target- and diversity-oriented synthesis of spiroketals. In contrast to most existing methods for spiroketal synthesis, this reaction does not rely upon thermodynamic control over the stereochemical configuration at the anomeric carbon. Stereochemically diverse glycals are first alkylated at the C1-position to introduce a hydroxyl-bearing side chain, then epoxidized stereoselectively. Treatment with Ti(Oi-Pr)4 leads to an unusual kinetic epoxide-opening spirocyclization (spirocycloisomerization) with retention of configuration at the anomeric carbon. The reaction is proposed to proceed via a chelation-controlled mechanism and has been used to form five-, six-, and seven-membered rings with stereochemically diverse substituents. This approach may also be useful for the related intermolecular beta-mannosidation reaction. This Ti(Oi-Pr)4-mediated spirocyclization is stereochemically complementary to our previously reported MeOH-induced spirocyclization, which proceeds with inversion of configuration, and together, these reactions provide comprehensive access to systematically stereochemically diversified spiroketals. 相似文献