乙醇在杂多酸上的氧化、脱水和程序升温脱附研究

合成了两个系列具有Keggin结构的12-钒钼磷酸和钨钼磷酸,研究了它们对乙醇氧化、脱水的催化反应。借助程序升温脱附技术研究了反应物及产物乙醇、乙烯、乙醚等在样品上的程脱作用。讨论了钨、钒取代部分钼原于后对杂多酸酸性及氧化性能的影响。     

土壤微生物ATP、脱氢酶和尿素酶活性的ED50值评价外源镧的生物毒性

０IntroductionRareearthsarenowappliedwidelyinChina，whichcanimprovecropsyieldsandthetheirqualit－ies犤１犦．Thebeneficialeffectsmaybeduetothestimu－latoryeffectsoftheseelementsonthenutrientuptakebyplantsorontheincreasingofchlorophyllsynthesisintheplants犤２犦．Whilealotofresearcheshavebeendoneontheimprovednutritionofcropsafterapplica－tionofrareearths，muchlessattentionhasbeenpaidtothedeteriorationofsoilqualityduetotheapplicationofrareearthsforyears犤３犦．Scientistshavediscoveredthataccumula…     

Studies on the refolding of the reduced-denatured insulin with size exclusion chromatography

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 L^t-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).     

Total synthesis of crotophorbolone

As a natural diterpenoid, crotophorbolone possesses a challenging trans,trans-5/7/6 framework decorated with six contiguous stereogenic centers and is structurally and biogenetically related to tigliane-type diterpenoids with intriguing bioactivities such as phorbol and prostratin. Based on the convergent strategy, we completed an eighteen-step total synthesis of crotophorbolone starting from (−)-carvone and (+)-dimethyl-2,3-O-isopropylidene-l-tartrate. The key elements of the synthesis involve expedient installation of the six-membered ring and the five-membered ring with multiple functional groups at an early stage, cyclization of the seven-membered ring through alkenylation of the ketone between the five-membered ring and the six-membered ring, functional group-sensitive ring-closing metathesis and final selective introduction of hydroxyls at C₂₀ and C₄.

Convergent total synthesis of crotophorbolone was accomplished in 18 longest linear steps. Observation of unexpected thermodynamic stability of a cis,trans-5/7/6 tricycle would benefit synthetic design of tigliane- and daphnane-related diterpenoids.     

Competitive adsorption and desorption of a bi-solute mixture: effect of activated carbon type

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.     

Ab initio studies on the thermolysis of azetidine

The reaction mechanism of the thermolysis of azetidine to form ethylene and methylen-imine has been studied by ab initio SCF MO method at STO--3G and 3-21G levels. Two possible step-wise pathways are explored. One is the breaking of C--C bond as the first step, while the other is thebreaking of C--N bond. All the stationary points on the potential energy surface (PES) are fully optimiz-ed. MP2 / 3-21G single point calculations on all stationary points and MCSCF / STO-3G computationsfor some stationary points are also carried out. The calculations indicate that azetidine decomposesvia biradicaloid intermediates and the cleavage of C--N bond is preferable to that of C--C bond.     

Formation and photoluminescence of silver nanoparticles stabilized by a two-armed polymer with a crown ether core

Silver nanoparticles were synthesized by the use of a two-armed polymer with a crown ether core [poly(styrene)]-dibenzo-18-crown-6-[poly(styrene)] based on the flexibility of the polymer chains and the complex effect of crown ether with Ag(+) and Ag. The size of silver nanoparticles could be tailored by controlling the initial concentrations of the polymer and Ag(+), and the molecular weight of the polymer. The emission of silver nanoparticles was blue-shifted, and the intensity of the photoluminescence of silver nanoparticles stabilized by the polymer was significantly increased due to the complex effect between the crown ether embedded in the polymer and the silver nanoparticles.     

Density functional theory study of the mechanism of the proline-catalyzed intermolecular aldol reaction

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     

Microstructure and electrical properties of BaTiO<Subscript>3</Subscript> and (Ba,Sr)TiO<Subscript>3</Subscript> ferroelectric thin films on nickel electrodes

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.     

Fabrication of lead titanate single crystalline nanowires by hydrothermal method and their characterization

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.