LiCl对Fe_2O_3/SiO_2甲烷氧化偶联反应的助催化作用

使用穆斯堡尔谱，ESR和XRD等技术表征了未添加助剂和添加LiCl的Fe2O3／SiO2催化剂．XRD结果指出，添加LiCl的Fe2O／SiO2催化剂出现铁酸盐和α-方石英的衍射峰，这种结果的出现与该催化剂有较高的C2烃选择性密切相关。穆斯堡尔谱结果表明：添加LiCl的Fe2O3／SiO2催化剂有更高的结构对称性．这种结构对分子氧的活化起着重要的作用．氯的存在大大降低了氧的离解吸附的速率，减少了原子氧的吸附位的数目，并可除去吸附的原子氧，该氧种对COx的生成有利．     

Pulse radiolysis of one-electron oxidation of rare tricyclic nucleoside derivative

~~Pulse radiolysis of one-electron oxidation of rare tricyclic nucleoside derivative@赵红卫$Shanghai Institute of Nuclear Research, Chinese Academy of Sciences! Shanghai 201800,China @江致勤$Department of Chemistry, Tongji Unviersity!Shanghai 200092,China @窦大营$Shanghai Institute of Nuclear Research, Chinese Academy of Sciences! Shanghai 201800,China @吴铁一$Shanghai Institute of Nuclear Research, Chinese Academy of Sciences! Shanghai 201800,China @王文锋$Shanghai…     

Molecular dynamics simulation of room-temperature ionic liquid mixture of [bmim][BF4] and acetonitrile by a refined force field

1-Butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]) is one of the promising room-temperature ionic liquids. To test the refined force field for [bmim][BF4] proposed in our previously work (J. Phys. Chem. B, 2004, 108, 12978-12989), thermodynamic properties of mixtures of [bmim][BF4](1)+ acetonitrile (2) are presented by using molecular dynamics over the whole concentration range. The calculated densities are in good agreement with the experimental data with deviations less than 2%, indicating the force field is applicable to the mixtures. In addition, the diffusion constants, viscosities, heats of vaporization, cohesive energy densities and excess properties of the mixtures are reported. The microscopic structures are discussed in detail, corresponding to the thermodynamic properties.     

Cr_2O_7~(2-)对B-Z振荡反应的影响及其分析应用

研究了Cr2O72-对B-Z化学振荡反应的影响.结果表明,Cr2O27-的加入明显改变该振荡反应的诱导期,且诱导期的改变值Δtin与所加入Cr2O72-的浓度有良好的线性关系,线性范围3.45×10-6~6.20×10-4mol·L-1,相关系数为0.9992,对Cr2O72-扰动B-Z振荡反应的机理进行了探讨.     

Electrocatalysis of Tryptophan at Multi-Walled Carbon Nanotube Modified Electrode

Acid-treated multi-walled carbon nanotubes (MWNTs) were immobilized on the surface of a glassy carbon electrode to form an MWNT-modified electrode. The electrocatalytic response of the modified electrode towards tryptophan (Trp) was investigated by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The results demonstrated that the modified electrode exhibited a high degree of catalytic activity towards the oxidation of Trp. An oxidation peak was obtained in Trp solution at the MWNT-modified electrode. Compared with a bare electrode, the peak current had obviously increased, and the peak potential had shifted in a negative direction. However, under the same conditions, no response was observed for other amino acids. The oxidation peak currents were proportional linearly to the concentration of Trp, a property which could be utilized to detect Trp. The determination conditions, such as the concentration, the composition and the pH values of the supporting electrolyte, accumulation time, as well as scan rate etc. were optimized. Under the chosen conditions, the DPV peak current is linear to the concentration of Trp in the range of 2.5×10^–7 to 1.0×10^–4molL^–1, and the detection limit is 2.7×10^–8molL^–1. Moreover, the detection is free of interference from other amino acids. The modified electrode has been successfully applied to determine the concentration of Trp in composite amino acid injections, and it displays excellent repeatability and higher sensitivity.     

Study of feed temperature control of chromatography using computional fluid dynamics simulation

Recently preparative high-performance liquid chromatography (HPLC) has been used more and more frequently to separate drugs and natural substances. However, large-scale HPLC easily tends to reduce the yield and purity of the product. Hydrodynamic and heat factors play an important roles. Generally, in a large-scale HPLC column, the tracer profile inside column will take on a parabolic shape because of the distributor, which will impact the separation performance of the column. With the inlet temperature suitably lower than the wall temperature, this situation could be improved to some extent. In this work, some experiments were conducted using HPLC, with a column 10 cm in diameter to determine the optimal temperature difference between wall and inlet temperatures. The wall temperature was fixed at about 30 degrees C and the inlet temperature varied from 15 to 30 degrees C. The flow-rate of the eluent, methanol, was 300 ml/min. The experimental result was simulated using CFD software FLUENT 4.4.4. The simulated temperature field fitted the experimental one very well and the simulated flow, temperature and tracer distribution inside column could provide good explanation of separation performance under different conditions. In addition, the simulation could at least approximately predict the optimal temperature difference.     

聚醚氨酯薄膜表面性质的反相色谱法研究

本文报道了用反相色谱法研究多嵌段聚醚氨酯与几种低分子化合物的相互作用,测定了表征相互作用的热力学参数。结果表明,由ESCA证明表面软段富集的聚醚氨酯的反相色谱行为主要决定于富集层与探针分子的相互作用;苯及几种烷烃和聚醚氨酯的偏摩尔混合热和它的溶度参数与软段组分的溶度参数差值有关。     

Controllable self-assembly of parallel gold nanorod clusters by DNA origami

We demonstrate the self-assembly of three types of parallel gold nanorod clusters using a rod-like DNA origami as the template.     

Novel solid-phase synthesis of 1,2-dialkoxyindoles

[reaction: see text] A novel solid-phase synthesis of 1,2-dialkoxyindoles on SynPhase lanterns is described. A unique C-C bond formation involving a nucleophilic displacement of a solid-bound aryl fluorine by dimethyl malonate afforded the arylnitro methyl ester, which upon treatment with tin(II) chloride dihydrate gave the N-hydroxyindolone. Alkylation of the N-hydroxyindolones afforded the corresponding N-hydroxy-2-alkoxyindoles, which were further alkylated to give the 1,2-dialkoxyindole. A library of 64 (8R(1) x 8R(2)) discrete 1,2-dialkoxyindoles was prepared using a color encoding technique on SynPhase A-series lanterns.