Ketones to amides via a formal Beckmann rearrangement in ‘one pot’: a solvent-free reaction promoted by anhydrous oxalic acid. Possible analogy with the Schmidt reaction

A variety of ketones can be directly converted into the secondary amides expected from a Beckmann rearrangement of the corresponding oximes in high yield, by heating them with hydroxylamine hydrochloride and anhydrous oxalic acid at ∼100°C for 4-12 h. (Aromatic aldehydes afforded mixtures of nitrile and amide.) The transformation is apparently (kinetically) driven by the coupled decomposition of oxalic acid (to CO+CO₂) via the fragmentation of an intermediate oxime mono-oxalate. However, an alternative pathway, mechanistically analogous to the Schmidt reaction, is not only equally likely but may well be general for the Beckmann rearrangement.     

Synthesis,Spectroscopic Properties and Crystal Structure of (C4N2H12)2Zr(C2O4)4·H2O

The title compound (C4N2H12)2Zr(C2O4)4·H2O 1 was synthesized by the reaction of ZrOCl2·8H2O, H2C2O4·2H2O and piperazinium in aqueous solution. Single-crystal X-ray analysis has revealed that compound 1 (C16H26N4O17Zr, Mr = 637.63) crystallizes in the monoclinic system, space group P21/c with a = 9.0425(3), b = 13.3844(3), c = 19.1191(5)A, β = 98.365(1)o, V = 2289.34(11) A3, Z = 4, Dc = 1.850 g/cm3, F(000) = 1304, μ = 0.577 mm-1, the final R = 0.0240 and wR = 0.0628 for 4386 observed reflections with I > 2σ(I). X-ray crystal-structure analysis suggests that compound 1 consists of [Zr(C2O4)4]4- anion and two protonated piperazinium cations. The anions are linked through hydrogen bonds of piperazinium. FT-IR and Raman spectra clearly show the existence of oxalate groups in the crystal lattice.     

旋涂法酸处理PEDOT∶PSS薄膜对OLED性能的影响

采用旋涂法对PEDOT∶PSS薄膜进行了酸处理,研究了不同方法处理PEDOT∶PSS薄膜对器件ITO/酸处理PEDOT∶PSS/NPB/Alq3/Li F/Al性能的影响。实验结果表明:用盐酸(草酸)处理PEDOT∶PSS薄膜时,以0.75 mol/L的盐酸(草酸)在120℃下退火15 min时性能更好,最大电流效率达到4.28 cd/A。并且盐酸、草酸处理PEDOT∶PSS薄膜制备器件比未处理PEDOT∶PSS薄膜制备器件的电流效率明显提高了34%。     

Effects of Chemical Heat Sink Generated by an Oxalic Acid Cooling Stream on Film-Cooling Effectiveness

Based on the theory of heat transfer enhancement, a novel film-cooling method for turbine blades that involves a chemical heat sink generated by the use of oxalic acid as a cooling stream has been proposed. Experiments were conducted on a flat plate with a row of 30° angled holes, and the conventional method using air as the cooling stream was examined for comparison. Overall, the results of this study demonstrate that the proposed cooling method involving an oxalic acid-induced chemical heat sink is more effective than the conventional method.     

草酸沉淀法制备细颗粒红色荧光粉Y2O3：Eu3+的发光特性

对草酸作为沉淀剂制备的细颗粒红色荧光粉Y₂O₃:Eu³⁺进行结构和发光特性研究,结果表明:其一次粒径为20～30nm,团聚尺寸D₅₀=0.53μm。该荧光粉最大激发峰位于252.2nm,较微米级荧光粉233nm红移了19.2nm;最大的发射峰位于612nm,与微米级的相比几乎没有差别。Eu³⁺离子的掺入构成了发光中心,其最佳掺杂的质量分数为9%,荧光粉发光的猝灭浓度由微米级的6%提高到9%。由于纳米晶存在表面缺陷和悬挂键,其亮度约为微米晶的70%左右,随着团聚尺寸的增加、煅烧温度的提高和助熔剂的加入,荧光粉的发光强度增大。包膜能部分消除表面缺陷和悬挂键,提高发光亮度。荧光粉的色坐标为x=0.6479,y=0.3442。     

气溶胶生长过程的微观动力学研究

气溶胶作为大气颗粒物的重要成分对大气环境以及人体健康均有重要影响.其中气溶胶的吸湿性作为影响其在大气中存活时间以及物理化学性质的重要因素受到广泛关注.目前对于气溶胶颗粒的吸湿性研究较为简单,对于气溶胶颗粒物微观结构对吸湿性的影响较少.本文根据Langmuir吸附模型、Fick扩散定律建立了单颗粒的气-粒作用模型,分析了气溶胶颗粒物的均匀分布结构(H2O/C2H2O4)以及非均匀分布结构(H2O/C2H2O4/H2SO4)对其吸湿性的不同影响。研究结果发现,气溶胶颗粒物的非均匀分布结构会影响其吸湿过程的快慢;对于理想流体构成的气溶胶分子,由于分子之间不存在分子间相互作用,因此气-粒间的水分子交换更快,颗粒物外侧浓度首先升高,接着在浓度差的作用下,内侧颗粒逐渐向外扩散,直至达到平衡;相较与大尺寸的颗粒,在相同体积比的条件下,小颗粒由于气溶胶颗粒物的接触角大,因此表面张力大,水分更难流失;此外,由于大尺寸的气溶胶颗粒物表面积体积比较小,因此颗粒失水速度低,需要更多的时间达到相平衡。     

Composition of Chemisorption Layers Forming on a Chromium Electrode in Sulfuric Acid Solutions of Formaldehyde and Formic,Oxalic, and Glyoxylic Acids

Surface layers that form on a chromium electrode after its contact with sulfuric acid solutions of formaldehyde, formic, oxalic, and glyoxylic acids at an open-circuit potential and in conditions of cathodic polarization at a potential of ?1.05 ± 0.10 V (NHE) are examined by an x-ray photoelectron spectroscopy method. The structure of the Cls line, which characterizes the binding energy of electrons of that level with the nucleus in products of interaction of said organic compounds with metal, is analyzed in detail. It is established that chemisorption products include substances with reduced oxygen-containing functional groups and hydrocarbon fragments. The degree of carbonation of chemisorption products, whose appearance is probably connected with electrocatalytic reduction and processes of polymerization of organic substances, is given an estimate.     

Sequential poly(ester amide)s based on glycine,diols, and dicarboxylic acids: Thermal polyesterification versus interfacial polyamidation. Characterization of polymers containing stiff units

Sequential poly(ester amide)s derived from glycine were synthesized by a two‐step method, involving a final thermal polyesterification. Molecular weights were in general higher than those obtained with the previously reported synthesis on the basis of interfacial polyamidation. Polymers with stiff units like oxaloyl or terephthaloyl residues were thermally characterized and their degradability studied by using different types of enzymes. Polymers containing short diols are degradable in papain solutions, the degradation rate being higher for oxalic derivatives. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 4283–4293, 2001     

以草酸为电子给体在Pt-TiO2上光催化生成氢

 以草酸为电子给体,研究了在Pt－TiO2上光催化生成氢的反应．草酸的存在明显促进了生成氢的反应;二氧化钛负载Pt也明显提高了反应速率,Pt的最佳负载量为w（Pt）＝0．5％．草酸浓度对氢生成反应的影响符合Lang－muir关系式．最佳pH值为2～4．     

食品及生物样品中痕量草酸的荧光动力学法测定

拟定了一个荧光动力学测定痕量草酸根的新方法。在硫酸介质中，草酸催化重铬酸钾氧化罗丹明６Ｇ使其荧光猝灭。方法线性范围为０．８－１４．０ｍｇ／Ｌ，直接用于菠菜，人尿中草酸根的测定，获得满意结果。