An Efficient Four‐component Synthesis of Spiro[indoline‐pyrazolo[4′,3′:5,6]pyrido[2,3‐d]pyrimidine]triones

A four‐component reaction in the presence of Alum [KAl(SO₄)₂·12H₂O] as an inexpensive and reusable catalyst using the ionic liquid as an effective green reaction media is reported.     

Co-crystallizing coordination compounds

Crystallization of an equimolar mixture of 1,10-dimethylphenanthroline (DMP) and manganese(II) chloride from N,N-dimethylformamide (DMF) has been studied. Rather than a useful route to a well-defined product, it was found that identical solutions could deposit crystals of three different compounds. The most common outcome was the formation of crystals of [MnCl₂(dmp)(dmf)], 1, or co-crystallization of [MnCl₂(dmp)(dmf)] and [{MnCl₂(dmp)}₂]. The co-crystals, 2, were always found to dissolve as crystals of 1 started to grow. Crystals of a third compound, [MnCl₂(dmp)₂], 3, were also isolated once.     

Biological evaluation of novel selenazole‐based compounds as potential thioredoxin reductase inhibitors

Recently, thioredoxin reductase as a target for treatment of tumors has attracted the attention of scientists. 1,2‐[Bis(1,2‐benzisoselenazolone‐3(2 H)‐ketone)]ethane (ethaselen, BBSKE, PCT: CN02/00412), designed and synthesized previously, is an effective thioredoxin reductase inhibitor; presently it is in phase II clinical trials, targeting gastric cancer, lung cancer and colon cancer. To seek more novel and effective anticancer drugs, we have developed many selenazole‐based compounds. Evaluation of the thioredoxin reductase inhibitory effect and investigation of the mechanism of anticancer drugs require abundant thioredoxin reductase, but since commercial thioredoxin reductase is expensive its use is often limited. Therefore, the preparation of thioredoxin reductase is necessary. Base on the above investigation, in this work we have prepared thioredoxin reductase and evaluated selenazole‐based compounds, and found that 44 compounds have high inhibitory effect on thioredoxin reductase with IC₅₀ < 10 µ m , of which 16 compounds have IC₅₀ values below 1 µ m . This is helpful in investigating and elucidating the mechanism of this kind of compound. Copyright © 2012 John Wiley & Sons, Ltd.     

某些含氮有机物光催化氧化产生的自由基中间体

本文用自旋捕捉技术与ESR相结合的方法研究了某些含氮有机物TiO₂光催化降解的过程中形成的活泼中间体.选择的化合物中有丁胺、戊胺、庚胺、六氢吡啶、吡啶、2-甲基吡啶、2,6-二甲基吡啶,这些分子中的氮原子分别作为初级脂肪胺、饱和环中的二级胺以及芳环中的三级胺出现,实验中观察到N-中心自由基及C-中心自由基与自旋捕捉剂加合物的ESR信号,表明这些自由基参与这些化合物光降解的初始过程,对深入了解其光降机理是有意义的.     

过渡金属化合物OsB2与OsO2低压缩性的第一性原理计算研究

利用基于密度泛函理论平面波赝势法的第一性原理计算,研究了过渡金属化合物OsB2和OsO2的金红石相、黄铁矿相与萤石相三种结构在高压下的状态方程和结构特性以及OsO2可能的高压相变.理论计算结果支持OsB2与OsO2的萤石相是潜在超低可压缩性的硬性材料.同时,也分析了它们的电子结构,力求理解大体变模量和高硬度的微观机制.结果表明,可以利用过渡金属高的价电子浓度,掺入硼、氧、碳、氮等轻的元素形成强的方向键,这可能提供了一种合成超硬材料的新途径.     

A comparative study on the interaction between tin(II) porphyrin and selected group 8B metals for potential application as reduction catalysts

We study the interaction between tin(II) porphyrin (SnPor) with platinum and non-precious Group 8B metals (iron, cobalt and nickel) by density functional theory and discuss the electronic properties of the resulting products. We also model the interaction of the resulting compounds with water where applicable. Our studies indicate that, SnPor-Ni possesses electronic properties similar to SnPor-Pt, suggesting that it may possess similar photocatalytic properties for reduction reactions, such as converting water to hydrogen gas.     

Low-Temperature Anti-Stokes Luminescence in Zn1-xMgxSe Mixed Crystals

Investigations of photoluminescence and Raman scattering in the ternary Zn_1-xMg_xSe compounds at 4.2 K were performed both in the Stokes and anti-Stokes regions using cw laser excitation with various wavelengths within the transparency band of the crystals. The anti-Stokes luminescence was observed for the first time in the ternary Zn_1-xMg_xSe compounds. We have found variations in the shape and position of the Stokes and anti-Stokes luminescence bands with an increase in the band gap energy, which depends on magnesium content. We assume that the anti-Stokes emission is generated by two-step excitation via deep-level centers. It is shown that the low-temperature anti-Stokes photoluminescence can probe the spatial distribution profiles of impurities in the bulk of crystals.     

Crystal structure and thermal behavior of two new organic monosulfates NH3(CH2)5NH3SO4 1.5H2O and NH3(CH2)9NH3SO4 H2O

The chemical preparation, the calorimetric studies and the crystal structure are given for two new organic sulfates NH₃(CH₂)₅NH₃SO₄ 1.5H₂O (DAP-S) and NH₃(CH₂)₉NH₃SO₄·H₂O (DAN-S). DAP-S is monoclinic P2₁/n with unit cell dimensions: a=11.9330(2) Å; b=10.9290(2) Å; c=17.5260(2) Å; β=101.873(1)°; V=2236.77(6) Å³; and Z=8. Its atomic arrangement is described as inorganic layers of units and water molecules separated by organic chains. DAN-S is monoclinic P2₁/c with unit cell parameters: a=5.768(2) Å; b=25.890(10) Å; c=11.177(5) Å; β=115.70(4)°; V=1504.0(11) Å³ and Z=4. Its structure exhibits infinite chains, parallel to the [100] direction where the organic cations are interconnected. In both structures a network of strong and weak hydrogen bonds connects the different components in the building of the crystal.     

Synthesis of Nanoscale Bimetallic Particles in Polyelectrolyte Membrane Matrix for Reductive Transformation of Halogenated Organic Compounds

Nanosized Fe/Ni and Fe/Pd particles were synthesized in the polyacrylic acid (PAA)/polyether sulfone (PES) composite membrane matrix for reductive transformation of halogenated organic compounds (HOCs). The advantages of using membrane to immobilize nanoparticles are the reduction of particles loss, prevention of particles agglomeration, and potential application of convective flow. Cross-linked PAA/PES composite membranes containing metal ions as particles precursor were prepared by heat treatment with ethylene glycol (EG) as a cross-linking agent. Nanoscale metal particles were formed and immobilized inside the membrane matrix after reduction with sodium borohydride. Membrane morphology and structure were observed by scanning electron microscopy (SEM). Particle size and distribution were characterized by SEM and transmission electron microscopy (TEM). Energy dispersive X-ray spectroscopy (EDS) was used to obtain the qualitative and quantitative element information of particles. A specimen-drift-free EDS line profile and EDS mapping system was performed in a scanning transmission electron microscopy (STEM) to determine the two-dimensional element distribution of iron and nickel in the nano domain. In the dechlorination study with trichloroethylene (TCE) as a representative HOCs, rapid and complete destruction of TCE was achieved by using nanosized bimetallic Fe/Ni or Fe/Pd in PAA/PES composite membranes. Typically more than 95% of 10 mg/l TCE was reduced within 1 h. Ethane was found in the headspace as the main product.