纵轴配位固载金属卟啉催化的环己烷氧化反应

由简单方法合成了ＰＶＣ,ＣＰＶＣ和Ａｌ２Ｏ３纵轴固载的氧桥连金属卟啉ＴＰＰＭ（Ⅲ）ＯＬ（Ｍ＝Ｆｅ,Ｍｎ;Ｌ＝ＰＶＣ,ＣＰＶ和ＡｌＯ３）并将它们用于温和条件下催化ＰｈＩＯ氧化环己烷的反应。实验结果表明,与未固载金属卟啉ＴＰＰＭ（Ⅲ）Ｃｌ比较,纵轴固载金属卟啉ＴＰＰＭ（Ⅲ）ＯＬ具有催化效率高,对产物的选择性强和重复使用性能好等优点。     

鸡蛋白四苯基钴卟啉催化氧气氧化乙醇

鸡蛋白中的转铁蛋白具有清除过氧自由离子的功能.为了考察这些蛋白质在金属卟啉催化剂催化氧化反应中是否有增效作用,用鸡蛋白固载金属卟啉制备了鸡蛋白四苯基钴卟啉固体催化剂,研究其催化氧化乙醇选择性生成乙醛和乙酸的能力,考察反应时间、温度和压力对其催化性能的影响,并用紫外可见光谱( UV-Vis)及傅立叶红外吸收光谱(FT-I...     

纳米孔壳聚糖固载四(p-磺酸基苯基)铁卟啉催化氧化乙苯

为了模拟细胞色素P-450酶催化活性空腔,最大发挥固载金属卟啉的催化活性功能。研究以纳米孔壳聚糖微球(np-CTS)作为载体,通过离子键接枝四(p-磺酸基苯基)铁卟啉(Fe TPPSO3H),制备相关的纳米孔壳聚糖固载金属卟啉仿生催化材料(Fe TPPSO3-H3+N-np-CTS)。采用紫外可见光谱(UV-Vis)、傅里叶红外光谱(FT-IR)、X-射线衍射技术(XRD)、差热分析技术(TG),比表面测试(BET)和扫描电镜技术(SEM)对该催化材料进行形态与结构的表征。研究其催化氧化乙苯性能。实验结果表明:在最佳的温度(140℃),压力(0.8 Mpa)和1 mg的催化剂(Fe TPPSO3H)用量反应条件下,催化剂可再重复使用4次,平均的乙苯转化率为52.72%,选择性为63.85%,醇酮产率为33.67%,催化剂转化数为3.39×106。与相应无孔的壳聚糖固载金属卟啉仿生催化材料及未固载金属卟啉的催化性能相比,其催化氧气氧化乙苯生成主要产物的收率分别提高9.54%和2.40%。这表明纳米孔壳聚糖固载四(p-磺酸基苯基)铁卟啉催化剂材料,具有更好的催化性能。     

多孔壳聚糖四(p-磺酸钠苯基)锰卟啉的制备及其催化性能

为研究多孔壳聚糖金属卟啉选择催化氧气氧化甲苯的能力,以壳聚糖通过盐键和配位键固载四(p-磺酸钠苯基)锰卟啉,用UV-Vis和FT-IR波谱技术、TEM和TG对该催化材料进行结构表征,在无外加溶剂和助催化剂条件下探索其催化性能。结果表明:在优化反应条件(温度180℃,压力0.8MPa)下,多孔壳聚糖四(p-磺酸钠苯基)锰卟啉催化氧化甲苯的转化率为15.3%,醛醇产率5.5%,多孔壳聚糖四(p-磺酸钠苯基)锰卟啉对甲苯的催化效能分别比无孔壳聚糖四(对-磺酸钠苯基)锰卟啉和四(对-磺酸钠苯基)锰卟啉的提高了16.8%和49.3%。壳聚糖通过盐键和配位键固载金属卟啉提高了金属卟啉的重复使用性能,并增强了催化甲苯的能力。     

鸡蛋白四苯基双铁卟啉催化氧气氧化乙醇

制备了鸡蛋白固载四苯基双铁卟啉催化剂,用紫外可见光谱(UV-Vis)及傅立叶红外吸收光谱(FT-IR)技术对其进行表征.研究了固载催化剂催化氧气氧化乙醇选择性生成乙醛和乙酸的能力,并对固载催化剂及纯鸡蛋白的催化能力比较.实验结果表明:在最佳反应条件下,鸡蛋白四苯基双铁卟啉催化乙醇氧化的转化率为18.43%,选择性(乙醛+乙酸)是63.5%.在相同条件下,鸡蛋白四苯基双铁卟啉比鸡蛋蛋白的催化活性高.固载的金属卟啉和鸡蛋白中的转铁蛋白共同起催化作用.     

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     

双核金属卟啉模拟细胞色素P-450催化环己烷单充氧反应的研究

合成了Fe(Ⅲ)-Fe(Ⅲ)3种双核金属卟啉配合物，用元素分析、紫外可见光谱进行表征，另外还有单核金属卟啉配合物和6个中间体．研究了这些双核金属卟啉模拟细胞色素P-450催化环己烷单充氧作用及金属卟啉在两种反应体系中催化性能的研究．同时还与单核金属卟啉的催化性能进行比较．实验结果表明，双核金属卟啉的催化活性随着两个金属卟啉之间碳链的增长而增长，反应体系的改变会引起金属卟啉催化活性的变化，总体上，双核金属卟啉的催化活性要高于单核金属卟啉．     

氧化石墨烯固载四(对-羧基苯基)锰卟啉催化氧化甲苯

为模拟细胞色素P-450酶催化活性空腔,提高昂贵金属卟啉的催化使用效率,采用改进的Hummers法制备氧化石墨烯,通过π-π非共价键以及配位作用制得氧化石墨烯固载四(对-羧基苯基)锰卟啉的仿生催化材料。采用红外可见光谱(FT-IR)、紫外可见光谱(UV-Vis)、热重分析(TG)、扫描电镜(SEM)、比表面积测试(BET)和X射线光电子能谱分析(XPS)等技术对此催化材料进行表征,并运用于催化氧化甲苯的性能研究。研究结果表明,在较优条件(170℃,0.8 MPa)下,用含0.5 mg四(对-羧基苯基)锰卟啉的催化材料催化氧气氧化甲苯可以重复使用4次,其催化氧化甲苯的平均转化率为12%,醇酮产率为5%,基本保持四(对-羧基苯基)锰卟啉对甲苯的催化活性。这表明氧化石墨烯对四(对-羧基苯基)锰卟啉的固载作用能提高金属卟啉的催化使用效率,降低金属卟啉核心催化剂的成本,具有较好的应用价值。     

硫化锌固载四(4-羧基苯基)锰卟啉催化性能研究

将四(4-羧基苯基)锰卟啉[Mn TCPP]固载到硫化锌[ZnS]上制备了固载锰卟啉催化剂[Mn TCPP/ZnS],用UV-Vis、FT-IR和TG技术对其进行了表征,并用此固载催化剂催化氧气氧化环己烷。结果表明:在最适宜反应温度和压力(160℃和0.8 MPa)条件下,硫化锌固载四(4-羧基苯基)锰卟啉可以有效重复使用4次,其环己烷转化率42.6%,酮醇产率18.6%,催化剂转化数6.0×105,比未固载的Mn TCPP具有更好的催化活性和重复使用性能。     

硫化镉固载四(4-羧基苯基)锰卟啉催化氧化环己烷

为了模拟细胞色素P-450酶中巯基的轴向配位作用功能,将四(4-羧基苯基)锰卟啉(Mn TCPPCl)固载到载体硫化镉上,得到硫化镉固载四(4-羧基苯基)锰卟啉(Mn TCPP/Cd S)催化材料。用电感耦合等离子体发射光谱法(ICP-AES)、紫外—可见光谱(UV-Vis)、红外光谱(FT-IR)、热重分析(TG)、扫描电镜(SEM)、比表面积测试法(BET)、X-射线光电子能谱(XPS)对催化材料的形态和结构进行表征,并考察其催化氧气氧化环己烷的性能。实验结果表明:在最佳反应条件(155℃,0.8 MPa,1 mg Mn TCPPCl)下,固载催化材料(Mn TCPP/Cd S)可以循环催化氧化环己烷9次,环己烷转化率22.04%,醇酮产率13.94%。与未固载的Mn TCPPCl相比,环己烷的转化率和酮醇产率分别提高9.16%和8.31%,表现出良好的催化性能和重复使用性,具有较高的工业应用价值。     

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     

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