4-烯丙氧基-2,6-二(N,N-二乙胺基甲基)吡啶钌配合物催化苯乙酮氢转移反应

以配体4-烯丙氧基-2,6-二(N,N-二乙胺基甲基)吡啶与三苯基膦氯化钌配位化合物生成新的钌催化剂,催化苯乙酮氢转移反应。考察温度、碱强度、底物浓度及产物等对反应的影响。研究结果表明:在N2气氛下,82℃,苯乙酮、钌配合物和KOH的初始摩尔比为250∶1∶12,反应6 h,苯乙酮的转化率达到99.8%,该催化剂具有很好的催化活性和稳定性。     

试剂5-（溴吡啶偶氮）-5-二乙氨基酚与钌（Ⅲ）的显色反应研究

研究了5-(溴吡啶偶氮)-5-二乙氨基酚与钌(Ⅲ)的显色反应.在pH=6.5的醋酸-醋酸盐缓冲溶液中,形成了配位比为1∶1的深红色二元配合物.λmax=554nm,表观摩尔吸光系数为ε=6.02×104L/mol.     

一步法合成3-苯甲酰基-5,7-二羟基黄酮及其合成条件的优化

以2,4,6-三羟基苯乙酮和苯甲酰氯为原料,一步反应合成到了高产率的3-苯甲酰基-5,7-二羟基黄酮,目标产物的结构用1HNMR、ESI-MS进行了表征,采用正交试验对合成工艺进行了优化,得到的最佳合成工艺为:吡啶和2,4,6-三羟基苯乙酮的摩尔数之比为4∶1,碳酸钾和2,4,6-三羟基苯乙酮的摩尔数之比为8∶1,反应温度60℃,该方法可经济、方便的合成3-苯甲酰基-5,7-二羟基黄酮.     

新型双酚铋配合物的合成及其在CO_2与环氧烷耦合反应的催化性能

合成了3种双酚铋配合物,并以4-二甲氨基吡啶(DMAP)为助催化剂利用其催化CO2与环氧丙烷(PO)进行耦合反应.系统探讨了催化剂用量、温度、CO2压力和时间对反应的影响,得出了最佳的反应条件为:反应物用量r(PO∶Cat∶DMAP)=1000∶2∶1,反应温度130℃,CO2压力2 MPa,反应时间5 h.在最佳条件下,双酚配体上取代基为吸电子的氯离子时催化活性最好.合成的环状碳酸酯的产率达90%以上,产物的选择性均达到100%.     

含羧酸的环金属化钌配合物的合成与表征

通过配位反应和水解反应合成了一种含2-(2,4-二氟)苯基-4-吡啶甲酸的新颖C,N-配位型环金属化钌配合物Ru-1,并通过核磁共振氢谱、红外和紫外-可见光吸收光谱对该配合物进行了表征.结果表明:核磁共振氢谱、红外光谱与Ru-1结构吻合;金属到配体的电荷转移跃迁(MLCT)吸收最大值位于524 nm,比水解前的配合物红移近50 nm.     

双吡啶单吡咯钌配合物与DNA的相互作用

三联吡啶钌配合物和DNA相互作用已有大量报道,但基于类三联吡啶配体,如双吡啶吡咯,稳定的金属配合物和DNA作用却鲜见报道.利用荧光光谱、圆二色谱(CD)和紫外-可见光谱等表征手段,研究了4个已知的双吡啶吡咯钌配合物与DNA结合性质： [(PDP)Ru(COD)X],其中HPDP＝2,5-bis(2’-pyridyl)pyrrolide,COD＝1,5-环辛二烯,X＝Cl－ (1), NO3(－) (2);[(PDP)Ru(COD)(H2O)](BF4) (3) ; [(PDPCl)Ru(COD)Cl] (HPDPCl＝2,5-bis(2’-pyridyl)-3,4-dichloropyrrolide(4).发现化合物1以经典嵌插方式和DNA结合,2和3可能为部分或非经典嵌插结合DNA,4主要以静电相互作用结合DNA.此外,通过MTT法考察了配合物1～4对人宫颈癌Hela细胞的体外细胞毒性.     

新型手性四氮镍(Ⅱ)配合物的合成、表征及催化苯乙酮不对称氢转移研究

合成了两个手性四氮配体,(S,S,S,S)-N,N’-二[2-(对甲苯磺酰胺基)-1,2-二苯基乙基]乙二胺(A)和(S,S,S,S)-N,N’-二[2-(对甲苯磺酰胺基)-1,2-二苯基乙基]丙二胺(B),及其手性镍(Ⅱ)配合物1和2,采用元素分析、1 H NMR、MS和IR对它们进行了表征.研究了手性配合物催化苯乙酮的不对称氢转移反应,考察了碱量和反应时间对催化活性的影响.     

不对称三邻菲咯啉钌(Ⅱ)配合物的合成及其性质

多吡啶钌 ( )配合物由于具有优越的光电转换性能 ,已广泛用于太阳能电池、光解水催化、化学发光和电化学发光等方面 [1 ,2 ] .把三联吡啶钌 ( )修饰在 Nafion膜内制成电化学发光传感器已有一些报道[1 ,2 ] ,目前较成功的 ECL 传感器是用溶胶凝胶方法制备的三联吡啶钌衍生化的脱乙酰壳多糖修饰电极 [4] .已有的研究表明 ,三菲咯啉钌 ( )与三联吡啶钌 ( )相比 ,前者的 ECL更强 [5] .为了制备更加高效的 ECL 传感器 ,我们设计并合成了一种 ECL 传感器活性材料 (如图 1所示 ) .图 1　不对称三邻菲咯啉钌钌 ( )配合物的合成1　实验1 .1…     

苯氧基亚胺钛化合物催化甲基丙烯酸丁酯聚合

3,5-二叔丁基水杨醛与苯胺缩合得到3,5-二叔丁基水杨醛缩苯胺配体1a;配体1a的钠盐与TiC l4.2THF反应得到相应的水杨醛亚胺钛配合物1;以色谱-质谱联用(GC/MS)、核磁共振氢谱(1H NMR)、元素分析等手段表征了中间化合物及配合物1;在三异丁基铝助催化下,钛配合物1高效催化甲基丙烯酸丁酯(BMA)本体聚合;在反应温度为60℃,BMA/三异丁基铝/钛配合物1(摩尔比为2 000∶20∶1)反应18 h,84.28%BMA转化为粘均分子量为12.80万聚甲基丙烯酸丁酯。     

Ru/ZrO2催化剂催化氨硼烷水解产氢研究

采用浸渍-化学还原法制备了Ru/ZrO2催化剂,并考察了钌负载量、硼氢化钠的用量、还原温度以及反应条件对催化剂Ru/ZrO2催化BH3NH3水解产氢的影响.结果 表明,在钌的负载量为0.4％,钌与还原剂硼氢化钠的物质的量比为1∶1.6,还原温度为303 K时,Ru微晶尺寸为3.2 nm,Ru/ZrO2催化剂催化BH3N...     

Markedness and its Interpretation in Language Use

Language markedness is a common phenomenon in languages, and is reflected from hearing, vision and sense, i.e. the variation in the three aspects such as phonology, morphology and semantics. This paper focuses on the interpretation of markedness in language use following the three perspectives, i.e. pragmatic interpretation, psychological interpretation and cognitive interpretation, with an aim to define the function of markedness.     

Features of Women's language

Language is a means of verbal communication. People use language to communicate with each other. In the society, no two speakers are exactly alike in the way of speaking. Some differences are due to age, gender, statue and personality. Above all, gender is one of the obvious reasons. The writer of this paper tries to describe the features of women＇s language from these perspectives： pronunciation, intonation, diction, subjects, grammar and discourse. From the discussion of the features of women＇s language, more attention should be paid to language use in social context. What＇s more, the linguistic phenomena in a speaking community can be understood more thoroughly.     

低渗透非均质砂岩油藏启动压力梯度研究

理论推导与室内实验相结合,建立了低渗透非均质砂岩油藏启动压力梯度确定方法。首先借助油藏流场与电场相似的原理,推导了非均质砂岩油藏启动压力梯度计算公式。其次基于稳定流实验方法,建立了非均质砂岩油藏启动压力梯度测试方法。结果表明:低渗透非均质砂岩油藏的启动压力梯度确定遵循两个等效原则。平面非均质油藏的启动压力梯度等于各级渗透率段的启动压力梯度关于长度的加权平均;纵向非均质油藏的启动压力梯度等于各渗透率层的启动压力梯度关于渗透率与渗流面积乘积的加权平均。研究成果可用于有效指导低渗透非均质砂岩油藏的合理井距确定,促进该类油藏的高效开发。     

On Tragic Consciousness In The Works By Ernest Hemingway

As an American modern novelist who were famous in the literary world, Hemingway was not a person who always followed the trend but a sharp observer. At the same time, he was a tragedy maestro, he paid great attention on existence, fate and end-result. The dramatis personae's tragedy of his works was an extreme limit by all means tragedy on the meaning of fearless challenge that failed. The beauty of tragedy was not produced on the destruction of life, but now this kind of value was in the impact activity. They performed for the reader about the tragedy on challenging for the limit and the death.     

Achieving Unusual States of Matter Under High Pressure

正The periodicity of the elements and the non-reactivity of the inner-shell electrons are two related principles of chemistry,rooted in the atomic shell structure.Within compounds,Group I elements,for example,invariably assume the+1 oxidation state,and their chemical properties differ completely from those of the p-block elements.These general rules govern our understanding of chemical structures and reactions.Using first principles calcula-     

Exchange-Correlation and Electronic Excitation Energies from Pairing Matrix Fluctuations

We have developed an adiabatic connection to formulate the ground-state exchange-correlation energy in terms of pairing matrix linear fluctuations.This formulation of the exchange-correlation energy opens a new channel for density functional approximations based on the many-body perturbation theory.We illustrate the potential of such approaches with an approximation based on the particle-particle Random Phase Approximation(pp-RPA).This re-     

Density Functional Theory for the Response of Periodic Systems to Electric Fields Based on the Vector Potential Approach

正The electronic and nuclear(structural/vibrational)response of 1D-3D nanoscale systems to electric fields gives rise to a host of optical,mechanical,spectral,etc.properties that are of high theoretical and applied interest.Due to the computational difficulty of treating such large systems it is convenient to model them as infinite and periodic(at least,in first approximation).The fundamental theoretical/computational problem in doing so is that     

On the Thermodynamic Limit for Responses to Static Electromagnetic Fields

For molecular systems,the quantum-mechanical treatment of their responses to static electromagnetic fields usually employs a scalar-potential treatment of the electric field and a vector-potential treatment of the magnetic field.Although the potential for each field separately is associated with the choice of an(unphysical)origin,the precise choice of the origin for the electrostatic field has little consequences for the results.This is different for the     

Call for Papers

<正>"The Journal of Shanghai Normal University:Mathematics"is published by Shanghai Normal University as regular issues of The Journal of Shanghai Normal University each year from 2014 in English.The editors-in-chief of the issues are professors Yuhao Cong and Maoan Han.The Journal of Shanghai Normal University was started in 1958 with     

Journal of Donghua University ( English Edition) Contents of Volume 31

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