纳米KMn8O16粉体的室温固相合成与表征

室温或近室温固相反应要求绿色化、清洁化[1,2]。我们以KMnO4和MnCl2·4H2O为原料,用室温固相氧化还原反应制备氧化锰粉体时,得到了一种对H2O2分解具有较高催化活性的纳米KMn8O16粉体,用XRD、SEM、IR等技术对其进行了表征,发现研磨时间对粉体性能有显著影响。1　实验部分1 1　粉体的制备按摩尔比(2∶3)准确称取一定量的分析纯KMnO4和MnCl2·4H2O,分别置于玛瑙研钵中充分研细,再混合研磨,固相反应立即发生,体系颜色逐渐加深,并有刺激性气体产生,充分研磨后70℃恒温12h,固相产物依次经水洗至中性、醇洗、抽滤,真空干燥得黑色粉…     

Optimization of Mass Transfer Processes in the Zone of the Air Electrode of a Fuel Cell with a Solid Polymer Electrolyte

A two-dimensional mathematical model for the transport of reactants in a fuel cell with a solid polymer electrolyte is developed. The model is used for analyzing spatial distributions of the concentration of reactants and current density over the cell. The effect of the catalytic-layer activity, reactant speed, bipolar-plate geometry, thickness and porosity of current collector and/or gas-diffusion sublayer, and the reaction mixture composition on the fuel cell efficiency is estimated theoretically and experimentally.     

Solid Phase Synthesis of 2-Substituted 1,3-Oxazin-6-ones Using Resin-bound Cyclic Malonic Acid Ester

A facile solid phase synthesis of 2-substituted 1,3-oxazin-6-ones using polymer-supported Meldrum‘s acid has been reported. Reaction of the resin-bound cyclic malonic acid ester with triethyl orthoformate and subsequent double substitution with amide, afforded the corresponding polymer-supported acylaminomethylene cyclic malonic acid ester, which upon thermal treatment led to 1, 3-oxazin-6-ones in good yields and with high purity.     

Influence of radiation on thin ZnS-Tb films

Changes in thin zinc-sulfide films under the action of the γ-radiation of Co⁶⁰ are studied by investigating electroluminescence spectra of terbium embedded in these films as a luminescent probe. It is shown that changes in the relation of the intensities of bands, a decrease in their halfwidth and the background component, and simplification of the spectrum are observed in a short-wave region of the Tb radiation spectrum that corresponds to⁵D₃→⁷F_j transitions. The same modification of the radiation spectrum is characteristic of ZnS films whose crystalline structure is ordered in the course of thermal annealing at a temperature of 350°C. Based on the analysis of the data obtained it is inferred that irradiating the ZnS films with small radiation doses of 10⁴–10⁵ rad leads to the ordering of their crystalline structure due to the elimination of one of the types of structural defects. Institute of Physics of Semiconductors, National Academy of Sciences of Ukraine, 45, Nauka Ave., Kiev-28, 252650. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 3, pp. 338–341, May–June, 1997.     

Solid phase synthesis of azapeptides using an automatic synthesizer

Peptides containing azaglycine located terminally or within the backbone have been prepared in the solid phase by means of an automatic synthesizer.     

四（对-羟基苯基）卟啉氧合配合物的室温固相合成，表征及氧合能力

采用固相反应合成了四羟基苯基卟啉与与Fe^2＋,Co^2＋金属离子的配合物,在室温下,将其与分子O2作用,提纯后得到两种固态氧合配合物．通过元素分析、红外光谱（IR）、核磁共振氢谱（^1HNMR）、电导、热分析（TG／DTA）、紫外光谱（UV）等测试手段确定了氧合配合物的组成为[Co·THPP·O2]（NO3）2·2H2O、[Fe·THPP·O2]Cl2·2H2O]，可知1mol配合物吸收了1molO2,采用失重法测定了氧合配合物中的配位氧,确定1mol金属配合物吸收1molO2形成超氧配合物．     

非晶硅薄膜的低温快速晶化及其结构分析

在镀铝的廉价玻璃衬底上高速沉积的非晶硅薄膜在不同的温度下退火10min.退火温度为500℃时,薄膜表面形成了硅铝的混合相,非晶硅薄膜开始呈现了晶化现象 退火温度为550℃时,大部分(约80%)的非晶硅晶化为多晶硅,平均晶粒尺寸为500nm 退火温度为600℃时,几乎所有的非晶硅都转化为多晶硅,其平均晶粒尺寸约为15μm.     

Effect of Hydrolysis Conditions on the Direct Formation of Nanoparticles of Ceria–Zirconia Solid Solutions from Acidic Aqueous Solutions

The effect of the cation concentration, hydrolysis temperature, and composition in the CeO₂–ZrO₂ system on the direct precipitation of ceria–zirconia solid solutions and the structure of the precipitates from acidic aqueous solutions of (NH₄)₂Ce(NO₃)₆ and ZrOCl₂ by hydrolysis under hydrothermal conditions were investigated. Nanometer-sized (8–10 nm) ceria–zirconia solid solution particles in a composition range of 0 to 60 mol% ZrO₂ were directly precipitated from the solutions with total metal cation concentration less than 0.2 mol/dm³ by simultaneous thermal hydrolysis at 150–240°C. The crystalline phase of the precipitates gradually changed from cubic and/or tetragonal to monoclinic with increasing the cation concentration of the solution from 0.2 to 0.8 mol/dm³ at the starting composition of 50 mol% ZrO₂ under hydrolysis condition of 150°C for 48 h, which was attributed to decrease in the supply of hydrolyzed Ce component caused by decrease in the hydrolysis ratio of (NH₄)₂Ce(NO₃)₆. Ceria–zirconia solid solutions containing large amount of ZrO₂ maintained high specific surface area and small-sized crystallite after heat-treatment at 900–1000°C for 1 h.     

An effect of application of chiral aluminium alkoxides and amides as adducts to zirconium catalyzed carbo- and cycloalumination of olefins

This paper is dedicated to a study of properties of the following novel optically active organoaluminium compounds (OACs): (1S,2S)-l,7,7-trimethyl-2-[(dialkylalumina)oxy]-bicyclo[2.2.1]heptanes and (1S)-N-(dialkylalumina)-6,7-dimethoxy-1-methyl-1,2,3,4- tetrahydroisoquinolines. The synthesis of the chiral OACs was carried out in the reaction of either natural camphor or salsolidine with both AlEt₃ and i-Bu₂AlH. The main goal of the research was to investigate the stereodifferentiating activity of the chiral OACs in the olefin carbo- and cycloalumination reactions, catalyzed by Cp₂ZrCl₂.     

Total synthesis of (±) maculalactone A, maculalactone B and maculalactone C and the determination of the absolute configuration of natural (+) maculalactone A by asymmetric synthesis

Maculalactones A, B and C from the marine cyanobacterium Kyrtuthrix maculans are amongst the only compounds based on the tribenzylbutyrolactone skeleton known in nature and (+) maculalactone A from the natural source possesses significant biological activity against various marine herbivores and marine settlers. We now report a concise synthesis of racemic maculalactone A in five steps from inexpensive starting materials. Maculalactones B and C were synthesized by a minor modification to this procedure, and the synthetic design also permitted an asymmetric synthesis of maculalactone A to be achieved in around 85% ee. The (+) and (−) enantiomers of maculalactone A were assigned, respectively, to the S and R configurations on the basis of the chiral selectivity expected for catecholborane reduction of an unsymmetrical ketone in the presence of Corey's oxazoborolidine catalyst. Surprisingly, it appeared that natural (+) maculalactone A was biosynthesized in K. maculans in a partially racemic form, comprising ca. 90-95% of the (S) enantiomer and 5-10% of its (R) enantiomer. Coincidentally therefore, the percentage enantiomeric excess of the product obtained from asymmetric synthesis almost exactly matched that found in nature.