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951.
A novel two-dimensional complex, [Cu(bbdc)(phen)]·(H2O)(bbdc = 2-bromo-1,4-benzenedicarboxylate dianion; phen = 1,10-phenanthroline), has been synthesized and structurally characterized by single crystal X-ray analysis. The crystal structure consists of infinite chains of [Cu2(
4-bbdc)]2+ units connected by bis-monodentate bbdc ligands, the coordination mode of which [
4-bbdc] is very rare in the phenyldicarboxylate complexes. The substituent group of bbdc is believed to be the growth key of this coordination network. 相似文献
952.
The refolding of the reduced-denatured insulin from bovine pancreas was investigated with the size exclusion chromatography (SEC). It was shown that the reduced-denatured insulin originally denatured with 7.0 mol L?1 guanidine hydrochloride (GuHCI) or 8.0 mol L?1 urea could not be refolded with a non-oxidized mobile phase. Although the oxidized and reduced glutathione (GSSG and GSH) were employed in the oxidized mobile phase, the reduced-denatured insulin still could not be renatured. However, in the presence of 2.0 mol Lt-1 urea in the oxidized mobile phase employed, the reduced-denatured insulin can be refolded with SEC, and the aggregation of denatured insulin can be diminished by urea. In addition, the disulfide exchange of reduced-denatured insulin also can be accelerated with GSSG/GSH in the oxidized mobile phase. The three disulfide bridges of insulin were formed correctly and the reduced-unfolded insulin can be renatured completely. The results were further tested with reversed-phase liquid chromatography (RPLC) and hydrophobic interaction chromatography (HIC). 相似文献
953.
CCl2自由基与H2O分子反应动力学研究 总被引:2,自引:0,他引:2
用213 nm激光光解CCl4产生CCl2自由基,用LP LIF技术测定了室温下基态CCl2自由基与H2O分子的反应速率常数为(5.45±0.95)×10-14 cm3•molecule-1•s-1.在G2MP2理论水平上计算了CCl2+H2O反应的最低单重态势能面,揭示了插入与加成 消除两种反应机理,得到了三个可能的产物通道:HCl+HClCO、HCl+trans ClCOH以及HCl+cis ClCOH.并用RRKM TST和传统过渡态理论计算了这三个通道的分支比及其温度效应.结果说明在低温下(273 K),插入机理的产物通道的分支比远大于加成 消除机理的产物通道, HCl+HClCO是主要产物,分支比为77.4%,其次是HCl+cis ClCOH,分支比为22.6%.而在高温下(3000 K),加成 消除机理的反应通道大于插入机理, HCl+trans ClCOH分支比为82.3%. 相似文献
954.
This study aims to clarify the effects of carbon activation type and physical form on the extent of adsorption capacity and
desorption capacity of a bi-solute mixture of phenol and 2-chlorophenol (2-CP). For this purpose, two different PACs; thermally
activated Norit SA4 and chemically activated Norit CA1, and their granular countertypes with similar physical characteristics,
thermally activated Norit PKDA and chemically activated Norit CAgran, were used. The thermally activated carbons were better
adsorbers for phenol and 2-CP compared with chemically activated carbons, but adsorption was more reversible in the latter
case. 2-CP was adsorbed preferentially by each type of activated carbon, but adsorption of phenol was strongly suppressed
in the presence of 2-CP. The simplified ideal adsorbed solution (SIAS) model underestimated the 2-CP loadings and overestimated
the phenol loadings. However, the improved and modified forms of the SIAS model could better predict the competitive adsorption.
The type of carbon activation was decisive in the application of these models. For each activated carbon type, phenol was
desorbed more readily in the bi-solute case, but desorption of 2-CP was less compared with single-solute. This was attributed
to higher energies of 2-CP adsorption. 相似文献
955.
956.
Transition structures associated with the C-C bond-formation step of the proline-catalyzed intermolecular aldol reaction
between acetone and isobutyraldehyde have been studies using density functional theory methods at the B3LYP/6-31G** computational
level. A continuum model has been selected to represent solvent effects. For this step, which is the stereocontrolling and
rate-determining step, four reactive channels corresponding to the syn and anti arrangement of the active methylene of the
enamine relative to the carboxylic acid group of l-proline and the re and si attack modes to both faces of the aldehyde carbonyl group have been analyzed. The B3LYP/6-31G**
energies are in good agreement with experiment, allowing us to explain the origin of the catalysis and stereoselectivity for
these proline-catalyzed aldol reactions.
Received: 2 April 2002 / Accepted: 18 July 2002 / Published online: 11 October 2002
Acknowledgements. This work was supported by research funds provided by the Ministerio de Educación y Cultura of the Spanish Government by
DGICYT (project PB98–1429). All the calculations were performed on a Cray–Silicon Graphics Origin 2000 of the Servicio de
Informática de la Universidad de Valencia. We are most indebted to this center for providing us with computer capabilities.
Correspondence to: L. R. Domingo e-mail: domingo@utopia.uv.es 相似文献
957.
Photocatalytic oxidation of water is a promising method to realize large-scale H2O2 production without a hazardous and energy-intensive process. In this study, we introduce a Pt/TiO2(anatase) photocatalyst to construct a simple and environmentally friendly system to achieve simultaneous H2 and H2O2 production. Both H2 and H2O2 are high-value chemicals, and their separation is automatic. Even without the assistance of a sacrificial agent, the system can reach an efficiency of 7410 and 5096 μmol g–1 h–1 (first 1 h) for H2 and H2O2, respectively, which is much higher than that of a commercial Pt/TiO2(anatase) system that has a similar morphology. This exceptional activity is attributed to the more favorable two-electron oxidation of water to H2O2, compared with the four-electron oxidation of water to O2. 相似文献
958.
Sandip Halder Theodor Schneller Rainer Waser Florian Thomas 《Journal of Sol-Gel Science and Technology》2007,41(3):203-207
Nickel thin films have been sputtered on standard Si/SiO2 substrates with TiO2 as an adhesive layer. The thermal stability of these substrates was analyzed. SEM images show an increase in grain size with
annealing temperature. They were found to be stable till 800°C, beyond which the nickel layer disintegrated. These substrates
were used for deposition of BaTiO3 and (Ba,Sr)TiO3 dielectric thin films under a reducing atmosphere. The dielectric thin films were processed with various pyrolysis and annealing
temperatures in order to optimize the dielectric properties. Increased pyrolysis temperatures showed an increase in the grain
size. Results on these nickelised substrates were finally compared with dielectric films deposited on platinized silicon substrates
under identical conditions but crystallized in an oxygen atmosphere. 相似文献
959.
Haoshuang Gu Yongming Hu Hao Wang Xiangrong Yang Zhenglong Hu Ying Yuan Jin You 《Journal of Sol-Gel Science and Technology》2007,42(3):293-297
Single crystalline nanowires of lead titanate (PbTiO3) were fabricated by hydrothermal method at 200°C using lead acetate and n-tetrabutyl titanate as starting materials, where sodium hydroxide was served as a mineralizer. Crystalline phases, microstructure
and optical properties of PbTiO3 nanowires were investigated. The PbTiO3 nanowires were uniform and continuous along the long axis, and were composed of single crystalline PbTiO3 with a tetragonal perovskite structure. The diameter of a single nanowire was around 12 nm and the length reached up to 3 μm.
The chemical composition of the samples and the valence states of elements were determined by X-ray photoelectron spectroscopy
(XPS). The ultraviolet/visible absorption spectroscopic investigation suggested that the absorption edge of optical transition
of the first excitonic state occurred at around 320 nm. A blue-green light emission peaking at about 471 nm (2.63 eV) is observed
at room temperature, and the intensity of this emission increased with increasing excitation wavelength. Oxygen vacancies
are responsible for the light emission of PbTiO3 nanowires. 相似文献
960.
Mátyás Milen László Hazai Pál Kolonits György Kalaus Lajos Szabó Ágnes Gömöry Csaba Szántay 《Central European Journal of Chemistry》2005,3(1):118-136
Transformation of β-carboline derivatives into optically active entities were studied and the de and ee values of the resulted compounds were detected.
Dedicated to Professor Károly Lempert on his 80th birthday. 相似文献