金属卟啉催化性能与金属原子电子构型关系

合成了三种具有不同电子排布的金属卟啉，ＴＰＰＦｅ（Ⅲ）Ｃｌ，ＴＰＰＣｏ（Ⅱ）和［ＴＰＰＦｅ（Ⅲ）］２Ｏ，并用它们模拟细胞色素Ｐ－４５０单充氧酶在温和条件下催化环己烷的氧化反应。结果表明，金属卟啉的仿生催化性能与它们的磁场性质有关。对ＰｈＩＯ氧化环己烷的反应，具有低自旋排布的ＴＰＰＣｏ（Ⅱ）和由于反铁磁耦合而呈现抗磁性的［ＴＰＰＦｅ（Ⅲ）］２Ｏ没有催化性能，而高自旋排布的ＴＰＰＦｅ（Ⅲ）Ｃｌ具有催化     

C_3A 的 Al-O,Ca-O 键与水化活性关系的量子化学研究

通过量子化学的ＳＣＣ－ＤＶ－Ｘα计算方法，分别研究了Ｃ３Ａ分子结构中２种ＡｌＯ４四面体和３种ＣａＯｘ（ｘ＝６，６，９）多面体的价键特性与活性。原子净电荷、键强、电子态密度、ＥＬＵＭＯ以及ΔＥ（ＬＵＭＯ－ＨＯＭＯ）等的计算结果表明：与水反应时，多面体活性大小顺序为Ｃａ（４）Ｏ９＞Ｃａ（１）Ｏ６（或Ｃａ（３）Ｏ６）＞Ａｌ（１）Ｏ４＞Ａｌ（２）Ｏ４。Ｃ３Ａ具有高水化活性主要与弱的Ｃａ－Ｏ键和空洞缺陷有关。     

尾式缬氨酸卟啉及其金属配合物的合成及催化性质研究

报道了５〔（对Ｎ缬氨酸丁氧基）苯基〕１０,１５,２０三（对氯苯基）卟啉（Ｈ２Ｌ）及其金属配合物ＭＬＣｌ（Ｍ＝Ｆｅ,Ｍｎ）的合成,并对其进行了元素分析、ＩＲ、ＵＶＣｉｓ及荧光光谱的结构表征．初步研究了在新的催化体系Ｏ２ＺｎＨＡｃＩｍ,ＭＬＣｌ对烯烃的催化环氧化．     

钌卟啉作为双功能模拟酶的研究

以３种钌卟啉［Ｒｕ（ＴＰＰ）（ＣＯ），Ｒｕ（ＯＥＰ）（ＣＯ），Ｒｕ（４－Ｃｌ－ＴＰＰ）（ＣＯ）］作为超氧化物歧化酶（ＳＯＤ）和过氧化氢酶（ＣＡＴ）双功能模拟酶。核黄素－蛋氨酸光照法证实它们在１０＾６￣１０＾５ｍｏｌ·Ｌ＾－１浓度范围内有清除Ｏ２·的作用；分光光度法证实它们能催化Ｈ２Ｏ２的分解，且分解率随浓度增大而增大；用小鼠肝匀浆法测定Ｒｕ（ＴＰＰ）（ＣＯ）、ＳＯＤ和ＣＡＴ，均表明具有较好的抗脂质     

MTPP－CeO_x－SiO_2催化NO_x还原

在密闭循环反应器中，于２９０℃下研究了ＣＯ存在下催化剂ＭＴＰＰ－ＣｅＯ＿ｘ－ＳｉＯ＿２（Ｍ＝Ｃｏ￣（２＋）、Ｎｉ￣（２＋）、Ｃｕ￣（２＋））催化还原ＮＯ或Ｎ＿２Ｏ的反应。催化ＮＯ还原的活性顺序是ＮｉＴＰＰ＞ＣｏＴＰＰ＞ＣｕＴＰＰ，而Ｎ＿２Ｏ还原和ＮＯ深度还原为Ｎ＿２的顺序是ＮｉＴＰＰ＞ＣｕＴＰＰ＞ＣｏＴＰＰ。ＮＯ＿ｘ还原的催化特性和ＭＴＰＰ的电化学氧化机理有关（取决于中心金属或卟啉环被氧化的次序）。ＣＯ不仅还原ＮＯ＿ｘ而且还促进载体Ｃｅ＿２Ｏ＿３物种的形成。探讨了ＮＯ催化还原的机理。     

聚四芳基锰卟啉催化氧化环己烷的性能

合成了在苯环２，５位带有不同取代基（ＣＨ３、ＣＨ３Ｏ、Ｃｌ、Ｂｒ或Ｈ）的６种聚四芳基锰卟啉ｐ－ＰｏｌｙＴ（２，５－２Ｒ）ＰＰＭｎＣｌ和ｍ－ＰｏｌｙＴＰＰＭｎＣｌ，考察了它们催化ＰｈＩＯ氧化环己烷的性能，结果表明：这些聚四芳基锰卟啉具有显著的抗氧化稳定性，带供电子基的聚合物催化速度较快，选择性较好     

五甲基茂基三苄氧基钛/MAO合成间规聚苯乙烯

比较茂基三苄氧基钛［ＣｐＴｉ（ＯＢｚ）３］／ＭＡＯ和五甲基茂基三苄氧基钛［Ｃｐ＊Ｔｉ（ＯＢｚ）３］／ＭＡＯ两种均相催化体系的苯乙烯间规聚合;发现由于Ｃｐ＊Ｔｉ（ＯＢｚ）３主配体茂基上取代甲基的供电子效应,Ｃｐ＊Ｔｉ（ＯＢｚ）３／ＭＡＯ催化体系有较强的热稳定性和较高的催化活性,在较高的温度下（７０℃）仍然能够合成粘均相对分子质量高达３．０×１０５的间规聚苯乙烯（ｓＰＳ）;研究了聚合温度、催化剂浓度和苯乙烯浓度对Ｃｐ＊Ｔｉ（ＯＢｚ）３／ＭＡＯ体系催化苯乙烯间规聚合的影响,最佳聚合条件为：聚合温度７０℃、催化剂浓度１．０４×１０－４ｍｏｌ／Ｌ、ｍ（Ａｌ）／ｍ（Ｔｉ）为８３０、ｃ（苯乙烯）＞４．３２ｍｏｌ／Ｌ．聚合反应产物用沸丁酮抽提８ｈ,不溶部分ｓＰＳ用ＧＰＣ,１３ＣＮＭＲ,ＦＴＩＲ,ＷＡＸＤ和ＤＳＣ等方法进行表征．     

Cl~- 和 SO_4~(2-) 对厌氧废水处理的抑制阈值

用人工配制高浓度有机废水分别研究了Ｃｌ－和ＳＯ２－４对厌氧生物废水处理的抑制作用和抑制阈值．在全混流厌氧恒化器和上流式厌氧污泥床（ＵＡＳＢ）反应器中分别得到了对厌氧消化基本无抑制作用（全混流恒化器：Ｃｌ－＜４．５ｇ／Ｌ,ＳＯ２－４＜１．８ｇ／Ｌ;ＵＡＳＢ：Ｃｌ－＜７．２ｇ／Ｌ,ＳＯ２－４＜３．０ｇ／Ｌ）;轻度抑制（全混流恒化器：Ｃｌ－＝４．５～６．０ｇ／Ｌ,ＳＯ２－４＝１．８～３．３ｇ／Ｌ;ＵＡＳＢ：Ｃｌ－＝７．２～８．２ｇ／Ｌ,ＳＯ２－４＝３．０～４．１ｇ／Ｌ）;中度抑制（全混流恒化器：Ｃｌ－＝６．０～１３．８ｇ／Ｌ,ＳＯ２－４＝３．３～６．５ｇ／Ｌ;ＵＡＳＢ：Ｃｌ－＝８．２～１０．０ｇ／Ｌ,ＳＯ２－４＝４．１～６．０ｇ／Ｌ）和重度抑制（全混流恒化器：Ｃｌ－＞１３．８ｇ／Ｌ,ＳＯ２－４＞６．５ｇ／Ｌ;ＵＡＳＢ：Ｃｌ－＞１０．０ｇ／Ｌ,ＳＯ２－４＞６．０ｇ／Ｌ）的不同Ｃｌ－和ＳＯ２－４浓度范围．     

~（27）AlNMR法研究PACS水中稀释形态分布

用２７ＡｌＮＭＲ方法研究了碱化度（Ｂ），Ａｌ３＋／ＳＯ摩尔比及水中稀释过程对ＰＡＣＳ（含ＳＯ的聚合氯化铝）结构的影响．实验结果表明，ＰＡＣＳ中铝含量大子０．９ｍｏｌ／Ｌ时，水中稀释对ＰＡＣＳ聚合度影响较大，小于０．９ｍｏｌ／Ｌ后水中稀释对ＰＡＣＳ聚合度影响较小．水中稀释可使聚合大分子向Ａｌ１３结构转化，这种转化能力的大小取决于ＰＡＣＳ中Ｂ的高低和Ａｌ３＋／ＳＯ摩尔比的大小．Ｂ的提高或ＳＯ含量的增加（Ａｌ３＋／ＳＯ摩尔比减小），都使这种转化能力有所增加．     

手性膦配位钯化合物的电化学性质

手性膦（Ｌ）配位的钯化合物ＰｄＣｌ２Ｌ２，Ｌ＝２－ＭＢＰＡ（１）；Ｌ＝３－ＭＢＰＡ（２），在ＤＭＦ中的循环伏安法电化学研究表明，二个化合物的氧还性质相近，与膦在Ｄ－醣上的碳取代位置无关．化合物的氧还反应有一个还原峰和两个氧化峰．比较化合物（２）在乙氰和ＤＭＦ中的ＣＶ图，显示两个氧化峰系由溶剂配位后的还原产物［ＰｄＬ２（Ｓｏｌｖｅｎｔ）２］１－氧化而得     

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.     

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     

An affordable accurate evaluation of the binding conformations predicted by molecular docking studies in bio-system

Franck-Condon factors bridge the gap between theoretical modeling and experimental observations for molecular electronic spectroscopy and electron transfer.Under the displaced harmonic oscillator approximation,multidimensional Franck-Condon factors are decomposed into a product of many one-dimensional(1D)Franck-Condon(FC)factors,and each 1D-FC factor is associated with one Huang-Rhys factor that determines the leading contribution of     

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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