多芳基取代咪唑的合成及其逆转多药耐药性研究

合成了一系列新的多芳基取代咪唑类化合物 ,其结构经元素分析、 IR、1 H NMR和 MS等确定 ,并采用 MTT法测定了它们对由 P-糖蛋白 ( P-gp)介导的肿瘤多药耐药性 ( MDR)的逆转效果 .结果表明 ,化合物 和 具有很好的体外逆转

多芳基取代蝶啶类化合物的合成及其抗肿瘤活性

目的研究多芳基取代蝶啶类化合物的合成及其抗肿瘤活性.方法由4,6-二氨基-5-亚硝基嘧啶衍生物与对-氨基苯乙腈衍生物通过环化合成目的物;采用MTF法测定目的物的抗肿瘤活性.结果设计、合成了9个新化合物(Ⅰ～Ⅲ),其结构经元素分析、IR,HNMR和MS等确定.化合物Ⅰ～Ⅲ的体外抗肿瘤活性较明显.结论化合物Ⅰ～Ⅲ显示了一定的体外抗肿瘤活性,但它们与小牛胸腺DNA之间并无明显作用,提示可能是通过抑制二氢叶酸还原酶(DHFR)或其他叶酸依赖性酶而起抗肿瘤作用.

多芳基酚聚氧乙烯醚磷酸酯盐的合成

以多芳基酚聚氧乙烯醚(PPE)和五氧化二磷为原料,合成了一种阴离子表面活性剂--多芳基酚聚氧乙烯醚磷酸酯三乙醇胺盐(TPEP),较佳的工艺条件为:n(PPE):n(P2O5 )为1.9:1, 添加剂0.5 g,四氯化碳15 mL, 酯化反应温度为65～70 ℃,反应时间5 h,单酯质量分数为61.3%,性能测试结果表明,这是一种良好的表面活性剂.

多芳基咪唑CPD的合成及与G-四链体相互作用研究

以4-氟苯甲醛为起始原料,通过安息香缩合反应、氧化反应、亲核取代反应以及Debus-Radziszewski咪唑合成反应等步骤,合成得到了多芳基咪唑CPD.^(1)H NMR、^(13)C NMR和HRMS确证其结构.紫外光谱实验和荧光光谱实验研究表明CPD对部分G-四链体具有一定的荧光识别作用,特别是可以识别c-myc G-四链体.单链DNA、双链DNA均不能使CPD的荧光产生增强,表现出较好的选择性.分子对接结果表明:CPD能堆积在G-四分体上,两条胺基侧链深入到G-四链体的负电性沟槽中,发生静电吸引作用,导致原有的分子构象发生变化,因而发射出荧光.

某些2-联萘基硼N,O双齿螯合物的质谱研究

本文报导含有2-联萘基的二芳基硼8-羟基喹啉类螯合物及苯丙氨酸螫合物的质谱研究。结果表明，这类化合物容易通过础上去烃化或经历从B-N键上的消除反应形成含三配位硼的硼杂FDA唑啉环。与2-联萘骨架相关的两类σ-π重排现象，即2-联萘骨架自身的π化重排以及包括硼原子在内的π-芳化也被探讨。后者涉及氢转移的同时逐出中性分子碎片（N，O-双齿配体）。

Ceria-modified hierarchical Hβ zeolite as a robust solid acid catalyst for alkenylation of p-xylene with phenylacetylene

A ceria‐modified hierarchical Hβzeolite was prepared by a desilication‐dealumination procedure followed by ceria modification.The catalytic performance of the ceria‐modified and unmodified hierarchical Hβzeolite catalysts for alkenylation of p‐xylene with phenylacetylene was investigated.Various characterization techniques,including X‐ray diffraction,X‐ray fluorescence,nitrogen adsorption‐desorption,and NH3temperature‐programmed desorption,were used to examine the structure‐performance relationships.Our results show that the optimized ceria‐modified hierarchical Hβzeolite catalyst demonstrated higher catalytic activity,selectivity,and stability for alkenylation of p‐xylene with phenylacetylene than those of pristine Hβzeolite.This performance was attributed to more acidic sites and improved accessibility to active sites through larger pores,together with a higher mesoporous surface area and volume resulting from the hierarchical pore architecture and ceria modification.Thus,our5wt%CeO2‐Hβ‐B0.2A0.2catalyst shows great potential for producing alkenyl aromatics through solid acid catalyzed alkenylation.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved

EPR and DFT Study of the Polycyclic Aromatic Radical Cations from Friedel-Crafts Alkylation Reactions

Electron paramagnetic resonance and electron-nuclear double resonance methods were used to study the polycyclic aromatic radical cations produced in a Friedel-Crafts alkylating sys- tem, with m-xylene, or p-xylene and alkyl chloride. The results indicate that the observed electron paramagnetic resonance spectra are due to polycyclic aromatic radicals formed from the parent hydrocarbons. It is suggested that benzyl halides produced in the Friedel-Crafts alkylation reactions undergo Scholl self-condensation to give polycyclic aromatic hydrocar- bons, which are converted into corresponding polycyclic aromatic radical cations in the presence of AlCl3. The identification of observed two radicals 2,6-dimethylanthracene and 1,4,5,8-tetramethylanthraeene were supported by density functional theory calculations using the B3LYP/6-31G（d,p）//B3LYP/6-31G（d） approach. The theoretical coupling constants support the experimental assignment of the observed radicals.

Numerical Investigation for the Effect of Unsaturated Aliphatic Hydrocarbons Addition on Precursors on Carbon Black

To investigate the effect of unsaturated aliphatic hydrocarbons on PAHs （polycyclic aromatic hydrocarbons） formation, numerical analysis using detailed reaction mechanism is performed. For the carbon black produced by benzene feedstock, three kinds of unsaturated aliphatic hydrocarbons （acetylene, diacetylene, and vinylacetylene） are added. The detailed reaction mechanism which is proposed by Wang and Frenklach is consisted by 527 reactions and 99 chemical species. The formations of PAHs and nuclei are promoted by unsaturated aliphatic hydrocarbons addition. There exits optimal benzene/acetylene ratio （XA/XB = 0.50）, benzene/diacetylene mixture ratio （XD/XB = 0.60）, benzene/vinyl-acetylene mixture ratio （XV/XB = 0.25）. The formation of nuclei is most promoted by acetylene addition, and the benzene/acetylene mixture ratio is 0.50.

Chemical Effects of CO2 Concentration on Soot Formation in Jet-stirred/Plug-flow Reactor

Soot formation was investigated numerically with CO2 addition in a jet-stirred/plug-flow reactor （JSR/PFR） C2H4/OJN2 reactor （C/O ratio of 2.2） at atmospheric pressure. An updated Kazakov mechanism empha- sizes the effect of the O2/CO2 atmosphere instead of an O2/N2 one in the premixed flame. The soot formation was taken into account in the JSR/PFR for C2H4/O2/N2. The effects of CO2 addition on soot formation in different C2H4/O2/CO2/N2 atmospheres were studied, with special emphasis on the chemical effect. The simulation shows that the endothermic reaction CO2 ＋ H - CO ＋ OH is responsible of the reduction of hydrocarbon intermediates in the CO2 added combustion through the supplementary formation of hydroxyl radicals. The competition of CO2 for H radical through the above forward reaction with the single most important chain branching reaction H ＋ O2, ＇ O ＋ OH reduces significantly the fuel burning rate. The chemical effects of CO2 cause a significant increase in residence time and mole fractions of CO and OH, significant decreases in some intermediates （H, C2H2）, polycyclic aromatic hydrocarbons （PAHs, C6H6 and CI6H10, etc.） and soot volume fraction. The CO2 addition will leads to a decrease by only about 5% to 20% of the maximum mole fractions of some C3 to Clo hydrocarbon intermediates. The sensitivity analysis and reaction-path analysis results show that C2H4 reaction path and products are altered due to the CO2 addition.

Polycyclic Aromatic Hydrocarbons in Nigerian Oil-based Drill-cuttings： Evidence of Petrogenic and Pyrogenic Effects

Compositional distribution and sources of polycyclic aromatic hydrocarbons （PAHs） in Nigerian oil-based drill-cuttings have been studied for evidence of petrogenic and/or pyrogenic effects with recommendations for the strict enforcement of the ban on the use of oil-based mud in drilling by government regulatory agencies and prior bio-treatment of the drill cuttings before final fate. A 4000 g mass of the drill cuttings obtained from a mud-pit close to a just-completed crude-oil well in the Niger Delta of Nigeria, 920 g of top-soil, which served as microbes and nutrients carrier and 154g of saw dust and poultry droppings were homogenized in a 10-litre plastic container of very low thermal conductivity. The mix ratio of cuttings to top-soil to saw-dust and poultry＇ droppings was 26：6：1. Mixing and watering of the reactors were done at 3 days interval under ambient temperature of 30 ℃ for 42 days. GC-FID results showed that the total initial PAHs concentration of the drill-cuttings was 223.52 mg/kg while the initial individual PAHs concentrations ranged from 1.67 to 70.7 mg/kg, dry weight, with a 90% predominance of the combustion-specific 3-mng PAHs. The ratio of anthracene to （phenanthrene ＋ anthracene） = 0.31 was found to be greater than the 0.10 source-criterion for PAHs fraction of molar-mass 178 g/mol while the ratio of fluoranthene to （pyrene ＋ fluoranthene） = 0.40 was found to be less than the 0.50 source-criterion for fraction of molar-mass 202 g/mol suggesting that the PAHs were from pyrogenic and petrogenic sources. Pyrogenic PAHs might be from a possible local heat effect while petrogenic PAHs might be from anthropogenic petroleum fractions in proprietary oil-based mud used in drilling. However, after bioremediation by composting, the total PAHs remaining in the drill cuttings were 4.25 mg/kg （representing a 98.1% reduction）. The half-lives of the PAHs in the medium ranged from 8 to 43 days.

Synthesis and Mollucicidal Activity of Some New Bicyclic and Polycyclic Pyrimidine Derivatives

Hydrazinolysis ofethylthiopyrimidine derivative 2 gave 2-hydrazinopyrimidine 3 which used as a convenient precursor for the synthesis of pyrazolylpyrimidines, hydrazones and pyrimidotriazines. Also, treatment of 2 with ethyl chloroacetate yielded N^-carbethoxymethyl-2-ethylthio-pyrimidine 15, which on reaction with ethyl carbazate and hydrazine hydrate afforded pyrimidotriazine and imidazopyrimidine, respectively. Chlorination of 2 using phosphorous oxycbloride yielded 4-chloropyrimidine 18, which reacted with some heterocyclic compounds having vicinal amino cyano groups to give some new polynuclear heterocyclic system. Also, the effect of some active methylene compounds on 18 was also studied. Some of the newly synthesized compounds were tested as mollucicidal agents against Biomphlaria alexandrina snails that caused intestinal bilharzias, the national problem in Egypt.

弱作用基有机发光材料

近年来,在非共轭甚至完全不含π电子的结构中发现的反常发光现象引起了人们的广泛关注.然而,由于其发光机制不清以及发光性能较差,导致这一领域的发展较为缓慢.总结了近年来在此类弱作用基发光材料的空间共轭机理研究及性能调控方面的最新研究进展.首先,基于非共轭多芳基烷烃机理研究模型,提出了弱作用基发光材料的空间共轭机制,并开发了空间共轭的构象和基元电子结构调控策略,基于这些策略成功开发出了高效率全光色发射的弱作用基发光聚合物.与此同时,研究发现空间共轭在传统具有共轭结构的扭转分子中也广泛存在,被认为是聚集诱导发光效应的一个重要发光机理.

Biotransformation of nitro-polycyclic aromatic compounds by vegetable and fruit cell extracts

Extracts from various vegetables and fruits were investigated for their abilities to reduce nitro-polycyclic aromatic hydrocarbons （NPAHs）. The extracts from grape and onion exhibited an interesting selectivity, yielding corresponding hydroxylamines or amines as major products under mild conditions of 30 ℃ and pH 7.0. Grape extracts reduced the 4-nitro-l,8-naphthalic anhydride with the highest conversion rate （〉99%） and the highest ratio of hydro- xylamine to amine （95：5）. In contrast, the onion extracts reduced 4-nitro-l,8-naphthalic anhydride with a conversion rate of 94% and a ratio of hydroxylamine to amine of 8：92. The thiol-reducing agent, 13-mercaptoethanol, and metal cations, Ca2＋ and Mg2＋, greatly increased the reductive efficiency. This work provides an alternative strategy for biotransformation of nitro-polycyclic compounds.

A simple catalyst for aqueous phase Suzuki reactions based on palladium nanoparticles immobilized on an ionic polymer

Palladium nanoparticles immobilized on a cross-linked imidazolium-containing polymer were evaluated as a catalyst for Suzuki carbon-carbon cross-coupling reactions using water as the solvent. The nanocatalysts show good catalytic activities for aryl iodides and aryl bromides and moderate activity with aryl chloride substrates. Coupling of sterically hindered substrates could also be achieved in reasonable yields. The heterogeneous catalyst is stable, can be stored without precautions to exclude air or moisture, and can be easily recycled and reused.

Quantification of selected monohydroxy metabolites of polycyclic aromatic hydrocarbons in human urine

An analytical method was developed to quantitatively determine selected monohydroxy metabolites of polycyclic aromatic hydrocarbons(PAHs) in human urine. The procedure included enzymatic hydrolysis to cleave the conjugated metabolites, solid-phase microextraction enrichment, and gas chromatography-mass spectrometry analysis. The method proved to be sensitive enough to detect the selected PAH metabolites in human urine.

Pyrene-based covalent triazine framework towards high-performance sensing and photocatalysis applications

Porous organic polymers(POPs)are an emerging class of porous materials,having many promising applications in a variety of areas.Among them,covalent triazine frameworks(CTFs)featuring conjugated and porous structures can be well applied in optoelectronics.To achieve high optoelectronic performance,usually the design and synthesis of CTFs based on appropriate building blocks is critical.Here we report the synthesis of two fluorescent CTFs based on typical fluorescent building blocks,in which CTF-Py constructed from a pyrene(Py)building block was reported for the first time,showing prospective applications in the sensing of nitroaromatics with high sensitivity,and photocatalytic water splitting and carbon dioxide reduction with high performance in comparison with other porous organic materials.