H3PW12O40/CNTs吸附-分解NOx及微波作用效果

将碳纳米管(CNTs)载体分别经混酸与硝酸蒸气预处理并在不同温度下煅烧, 然后分别采用浸渍法及机械研磨法负载磷钨酸(HPW), 制备出HPW/CNTs催化剂, 对比考察了上述催化剂对NOx的吸附与分解效果. 在空速为10000 h-1、 吸附温度为200℃的条件下, 用0.5 g催化剂对1696 mg/m3的NOx进行吸附实验, 结果表明, 以硝酸蒸气预处理且经300℃煅烧后的CNTs为载体, 采用机械研磨负载法制备的催化剂HPW/CNTs对NOx的吸附率与吸附能力最高, 分别为54%与16.6 mg NOx/(g\5h). 对吸附NOx后的催化剂体系进行了催化分解NOx的程序升温脱附-质谱(TPD-MS)研究, 结果表明, 所吸附的NOx在快速升温过程中发生分解, 在此过程中有氧产生, 分解产物包括N2, O2及N2O. 采用电阻炉快速加热与微波辐射2种方式分别对吸附的NOx进行催化分解, 结果表明, 微波功率为700 W时, NOx分解为N2的收率为33.3%, 高于电阻炉以150℃/min快速升温的N2收率. 使用过的催化剂通水蒸气后可实现再生, 对再生后的催化剂进行循环使用研究, 结果表明, 再生后的催化剂吸附与催化分解NOx的性能未有明显下降.     

Mn（OAc）2/Schiff base as a new efficient catalyst system for the Henry reaction of nitroalkanes with aldehydes

A series of novel Schiff bases bearing triazole structure were synthesized and characterized by IR and NMR.Mn（OAc）₂/Schiff base efficiently catalyzed Henry reaction of nitroalkanes with aldehydes to produce the corresponding products of β-nitroalcohols, under mild conditions with high yields（up to 99%）.A reaction mechanism is proposed based on the experimental results.     

Molecular dynamics study on the relationships of modeling, structural and energy properties with sensitivity for RDX-based PBXs

In this paper,a primary model is established for MD(molecular dynamics) simulation for the PBXs(polymer-bonded explosives) with RDX(cyclotrimethylene trinitramine) as base explosive and PS as polymer binder.A series of results from the MD simulation are compared between two PBX models,which are represented by PBX1 and PBX2,respectively,including one PS molecular chain having 46 repeating units and two PS molecular chains with each having 23 repeating units.It has been found that their structural,interaction energy and mechanical properties are basically consistent between the two models.A systematic MD study for the PBX2 is performed under NPT conditions at five different temperatures,i.e.,195 K,245 K,295 K,345 K,and 395 K.We have found that with the temperature increase,the maximum bond length(L max) of RDX N N trigger bond increases,and the interaction energy(E N-N) between two N atoms of the N-N trigger bond and the cohesive energy density(CED) decrease.These phenomena agree with the experimental fact that the PBX becomes more sensitive as the temperature increases.Therefore,we propose to use the maximum bond length L max of the trigger bond of the easily decomposed and exploded component and the interaction energy E N-N of the two relevant atoms as theoretical criteria to judge or predict the relative degree of heat and impact sensitivity for the energetic composites such as PBXs and solid propellants.     

Facile synthesis of ultra-long Cu microdendrites for the electrochemical detection of glucose

Ultra-long Cu microdendrites (MDs) were prepared by one-step electrodeposition on a glassy carbon electrode. The results demonstrated that the reduction potential, pH, and temperature of the electrolysis solution, as well as the amount of Cu²⁺ and citrate ions, play important roles in the formation of the Cu MDs. Notably, the X-ray diffraction experiments confirmed that the aggregations of the Cu nanocrystals preferred to grow along (111) direction. In addition, the resulting Cu MDs-modified electrode showed good electrochemical performance as a non-enzyme glucose sensor in alkaline media.     

Ferroferric oxide/chitosan scaffolds with three-dimensional oriented structure

A facile approach to construct ferroferric oxide/chitosan composite scaffolds with three-dimensional oriented structure has been explored in this research.Chitosan and ferroferric oxide are co-precipitated by using an in situ precipitation method,and then lyophilized to get the composite scaffolds.XRD indicated that Fe₃O₄ was generated during the gel formation process,and increasing the content of magnetic particles could destruct the crystal structure of chitosan. When the content of magnetic particles is lower than 10%,the layer-by-layer structure and wheel spoke structure arc coexisting in the scaffolds.Increasing the content of magnetic particles,just layer-by-layer structure could be observed in the scaffolds.Ferroferric oxide particles were uniformly distributed in the matrix,the size of which was about 0.48μm in diameter,2μm in length.Porosity of magnetic chitosan composite scaffolds is about 90%.When the ratio of ferroferric oxide to chitosan is 5/100,the compressive strength of the material is 0.4367 MPa,which is much higher than that of pure chitosan scaffolds,indicating that the layer-by-layer and wheel spokes complex structure is beneficial for the improvement of the mechanical properties of chitosan scaffolds.However,increasing the content of ferroferric oxide,the compressive strength of scaffolds decreased,because of the decreasing of chitosan crystallization and aggregation of magnetic particles as stress centralized body.Another reason is that the layer-by-layer and wheel spokes complex structure makes bigger contributions for the compressive strength than the layer-by-layer structure does.Three-dimensional ferroferric oxide/chitosan scaffolds could be used as hyperthermia generator system,improving the local circulation of blood, promoting the aggradation of calcium salt and stimulating bone tissue regeneration.     

Synthesis and antitumor activity of 1-acetyl-3-(4-phenyl)-4,5-dihydro-2-pyrazoline-5-phenylursolate and 4-chalcone ursolate derivatives

New 4-chalcone ursolate and 1-acetyl-3-(4-phenyl)-4,5-dihydro-2-pyrazoline-5-phenyl ursolate derivatives were synthesized by esterification of UA and chalcone or pyrazoline. The compounds were structurally confirmed by IR, ¹H NMR, ¹³C NMR, and HR-MS spectroscopy. The cytotoxicity of ten derivatives was evaluated against A549, SKOV3, and HepG2 cell lines by MTT assay. The result showed that several compounds were more potent than UA against A549 and SKOV3 cells; however, none of them were more potent than UA against HepG2.     

高效液相色谱-串联质谱法检测奶中克拉维酸残留

采用高效液相色谱-串联质谱(HPLC-MS/MS)建立了克拉维酸在奶中的残留检测方法。2 g样品经乙醇沉淀蛋白质后,转入鸡心瓶中旋转蒸发浓缩至0.5 mL左右,用乙酸铵定容,净化后检测。流动相为乙腈和0.1%甲酸水,梯度洗脱,经Luna 5u C8色谱柱分离,采用电喷雾电离,多反应监测负离子模式对克拉维酸进行定量分析。采用基质匹配法对奶中克拉维酸的含量进行标准校正,在克拉维酸含量为10～400 μg/kg范围内呈现良好的线性关系,相关系数大于0.999;奶中加标样品的检出限(LOD,按信噪比(S/N)≥3计)为10 μg/kg,定量限(LOQ, S/N≥10)为20 μg/kg。在定量限、1/2最高残留限量、最高残留限量、2倍最高残留限量添加水平下,奶中克拉维酸的平均回收率为80.00%～91.25%,相对标准偏差为5.60%～8.77%。该方法可用于奶中克拉维酸残留的分析检测。     

基于偶氮苯-4,4′-二甲酸配体的锰(Ⅱ)配合物的合成、晶体结构及性质研究(英文)

利用水热反应合成了一种新的锰配合物[Mn(ADB)(phen)(H2O)2]n(1)(H2ADB=偶氮苯-4,4′-二甲酸,phen=邻菲啰啉),运用元素分析、红外光谱、热重分析、电化学等方法对它进行了研究,并通过X射线单晶衍射测定了配合物的单晶结构。晶体结构表明,配合物属三斜晶系,空间群为P1,晶胞参数a=0.762 00(13)nm,b=0.915 30(15)nm,c=1.826 2(2)nm,α=88.467(3)°,β=84.145(2)°,γ=77.542(2)°。配合物1的中心锰离子是六配位,具有扭曲的八面体结构,偶氮苯-4,4′-二甲酸连接相邻的锰离子形成了一维"之"字链,进而链与链之间通过π-π堆积和氢键相互作用拓展成三维超分子结构。磁学性质研究表明该配合物为反铁磁性。     

钙调素与靶蛋白结合模式的多样性

钙调素(CaM)通过与数百种靶蛋白结合,调节众多钙信号通路参与的生理活动。钙调素与靶蛋白的结合模式也是多种多样的,数年前就有多篇这方面的综述发表,最近的一篇发表于2006年。这之后的5、6年,又有大量钙调素-靶蛋白复合体的结构以及新型的结合模式发表,这其中就包括本实验室发表的钙调素与钙调蛋白磷酸酶(CN)的钙调素结合区(CBD)结合的晶体结构,为不同于经典模式的X形二聚体。本文在前人综述的基础上,结合本实验室的成果,以及其他近5、6年新发表的结构,从经典包围型、其他包围型、伸展型、IQ基序相关、二聚体型、大分子参与的结合模式共6个类别,讨论了30多种钙调素-靶蛋白复合体的结构。这些多样的结合模式为钙调素调节功能的多样性提供了结构基础,也为解析结构未知的钙调素-靶蛋白复合体提供了启示。     

中国近代化学教育家——张贻侗

张贻侗是中国近代著名的化学教育家。他对北京师范大学、北平大学、西北师范大学及西北大学的化学教育作出了积极贡献,同时他也积极投身科学普及工作。本文介绍了张贻侗的生平简历、科学成就及其思想,以纪念这位对中国化学高等教育做出杰出贡献的化学家。