钴(Ⅱ)镍(Ⅱ)超分子配合物的微波合成、晶体结构

本文采用微波加热技术合成两种新的超分子配合物[Co(OBT)(2,6-pdc)(H2O)2].3H2O(1)和[Ni(OBT)(2,6-pdc)(H2 O)2].2H2 O(2)(2,6-H2 pdc=2,6-吡啶二羧酸,HOBT=1-羟基苯并三唑),并由X-射线单晶衍射分析确定了它们的晶体结构.配合物1属于三斜晶系,P-1空间群,晶胞参数:a=0.670 00(13)nm,b=1.008 0(2)nm,c=1.010 0(2)nm,α=104.21(3)°,β=106.91(3)°,γ=94.94(3)°,V=0.623 5(2)nm3,Z=2.配合物2属于三斜晶系,P-1空间群,晶胞参数:a=0.758 33(15)nm,b=1.133 3(2)nm,c=1.153 1(2)nm,α=104.74(3)°,β=106.63(3)°,γ=95.17(3)°,V=0.904 0(3)nm3,Z=2.配合物1和2中,中心原子钴和镍均为六配位八面体构型,两个配合物中均存在氢键作用和π-π堆积作用,使得配合物1和2扩展为三维超分子结构.     

以邻菲罗啉为辅助配体的一维Cu(Ⅱ)配合物结构及磁性表征

采用水热法合成了以叠氮钠和邻菲罗啉为配体的一维链状Cu(Ⅱ) 配合物,并通过元素分析、红外光谱、X射线单晶衍射和变温磁化率等技术对配合物进行了表征.该配合物属于三斜晶系,P1空间群,a=1.036 4(2),b=1.199 3(2),c=1.548 1(3)nm,α =87.70(3)°,β =84.58(3)°,γ =79.38(3)°,Z =1,V=1.882 3(7)nm3,d =1.735 mg/m3,F(000) =900.对该配合物的磁学性质进行了讨论.     

2,3-戊烷二酮二肟双核铜配合物的合成、结构与性质研究

2,3-戊烷二酮二肟(PDOH_2)与Cu(Ⅱ)离子在氯离子存在下反应得到配合物[Cu_2(PDOH_2)_2Cl_2]Cl_2.晶体结构表明,配合物为氯离子桥联双核Cu(Ⅱ)配合物.配合物属于三斜晶系,a=0.779 42(16)nm,b=0.811 72(16)nm,c=0.832 82(17)nm,α=102.76(3)°,β=103.38(3)°,γ=114.18(3)°,Z=1.变温磁化率测试结果表明,双核铜(Ⅱ)离子之间存在铁磁相互作用.     

碘桥联的氮氧自由基-铜配合物的合成与性质

氮氧自由基与Cu(Ⅱ)离子反应,在碘离子存在的情况下,得到了两个配合物[Cu2(NIT3-Py)4I2](1)与[Cu2(IM3-Py)4I2](2)[NIT3-Py:2-(3'-吡啶基)-4,4,5,5-四甲基咪唑啉-3-氧化-1-氧基自由基;IM3-Py:2-(3'-吡啶基)-4,4,5,5-四甲基咪唑啉-1-氧基自由基).晶体结构分析表明,两个配合物均为碘离子桥联Cu(I)形成的双核配合物,氮氧自由基作为端基配体与Cu(I)离子配位.配合物(1)属三斜晶系,空间群P1,a=0.736 90(6)nm,b=1.327 26(9)nm,c=1.438 86(14)nm,α=87.186(12)°,β=88.759(11)°,γ=80.612(11)°,Z=1.配合物(2)属单斜晶系,C2/c空间群,a=3.714 9(9)nm,b=0.725 83(19)nm,c=2.696 3(7)nm,β=129.967(3)°,Z=4.变温磁化率研究表明配合物(1)中存在弱的反铁磁相互作用.     

吡唑-3-甲酸配合物的合成、结构及性质研究

选用吡唑-3-甲酸为主配体,通过溶剂热法合成出两种配合物{[Ag_3(3-PCA)_3][Ag(DMAP)_2]_3}·10H_2O(1)和[Cu_2(3-PCA)_2(DMAP)_4]·2H_2O(2)(3-PCA=pyrazole-3-carboxylic acid,DMAP=4-Dimethylaminopyridine).用X射线单晶衍射仪测定了它们的晶体结构,并进行了红外表征.结果显示,配合物(1)为单斜晶系,空间群为Pc,晶胞参数为a=0.9409(8)nm,b=1.3411(8)nm,c=2.8699(2)nm,Z=2,V=3.6215(5)nm~3;配合物(2)属于三斜晶系,空间群为Pī,晶胞参数为a=0.8999(14)nm,b=1.0870(18)nm,c=1.1050(17)nm,α=78.426(14)°,β=68.732(15)°,γ=87.237(13)°,Z=1,V=0.9865(3)nm~3.对配合物(1)进行了固态荧光测试,结果表明其具有荧光性质;对配合物(2)进行了生物活性研究,结果表明该配合物可与BSA相互作用.     

[Cd2(BHP)2(2,6-pda)2(H2O)2]·H2O配合物的合成、结构及荧光性质

用溶剂热法合成了含混合配体的双核镉配合物[Cd2(BHP)2(2,6-pda)2(H2O)2]·H2O(BHP=吡啶2,6-二甲酰肼,2,6-H2pda=吡啶-2,6-二甲酸),用红外光谱和元素分析对配合物进行了表征.X-射线单晶结构分析表明,该配合物属于三斜晶系,空间群为Pi,晶胞参数:a=0.999 70(13) nm,b=1.038 00(15) nm,c=1.077 40(16)nm,α=115.601(3)°,β=110.510(3)°,γ=98.416(2)°,V=0.883 7(2) nm3,Z=1.配合物中的两个Cd(Ⅱ)离子都处于七配位的五角双锥几何构型中,配合物通过分子间的氢键作用形成了三维超分子结构,并对配合物的荧光性质进行了研究.     

[Mn(phen)3](ClO4)2·CH3OH的合成和晶体结构

合成了配合物[Mn(phen)3](ClO4)2.CH3OH,并用元素分析和IR对其进行表征。晶体结构分析结果表明该配合物属三斜晶系,空间群P-1,晶胞参数:a=1.12999(7)nm,b=1.28361(8)nm,c=1.44948(9)nm,α=85.385(1)°,β=76.134(1)°,γ=69.890(1)°,Z=4;该配合物的化学式为C37H37Cl2MnN6O9,Mr=834.9,中心金属离子Mn(Ⅱ)为六配位变形八面体构型。配合物通过1,10-邻菲口罗啉芳环间π-π堆积作用和分子间氢键形成了稳定的三维网状结构。     

新型有机-无机杂化杂金属多核配合物[Cd2(CuL)4(V4O12)]·2CH3OH·2H2O的合成与晶体结构

以偏钒酸、大环草酰胺配合物CuL(L=2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-diene)为共配体,利用液液扩散法设计并合成了有机-无机杂化杂金属多核配合物[Cd2(CuL)4(V4O12)]·2CH3OH·2H2O(1).通过元素分析、红外光谱及X射线单晶衍射等方法进行了结构表征.结果表明:该配合物属于三斜晶系,P-1空间群;晶胞参数a=1.048 48(17) nm,b=1.331 7(2) nm,c=1.603 0(3) nm,α=93.662(2)°,β=104.084(2)°,γ=107.987(2)°,V=2.041 3(6) nm3,Z=1.其结构为通过大环草酰胺、V4O124-的配位作用构成的中心反对称的十核杂三金属Cd2 Cu4 V4配合物.     

基于吡啶-4-甲酸组装的氢键型三维超分子体系及其密度泛函的研究

采用水热法合成了2种新型超分子配合物[Cu(C6H4O2N)2(H2O)4](1)和[Cd(C6H4O2N)2(H2O)4](2), 通过元素分析、红外光谱、热分析、X-射线衍射等技术对其进行了表征.2种配合物均属三斜晶系,空间群P1,配合物1晶胞参数a=0.776 9(2)nm,b=0.918 6(2)nm,c=1.072 5(3)nm,α=92.905(4)°,β=95.024(4)°,γ=111.117(3)°,V=0.708 5(3)nm3,Z=2,Mr=379.81,Dc=1.780 g/cm3,F(000)=390,μ=1.589 mm-1,最终偏离因子R1=0.022 4,R2=0.067 5;配合物2晶胞参数a=0.643 94(12)nm,b=0.695 98(13)nm,c=0.941 53(18)nm,α=94.878(3)°,β=104.733(3)°,γ=111.986(2)°,V=0.370 69(12)nm3,Z=1,Mr=428.67,Dc=1.920 g/cm3,F(000)=214,μ=1.518 mm-1,最终偏离因子R1=0.027 3,R2=0.074 6.配合物的中心原子M2 (M2 =Cu2 ,Cd2 )与2个吡啶-4-甲酸根及4个H2O配位,形成具有畸变八面体构型的基本结构单元,相邻单元通过O-H...O氢键的相连拓展为三维超分子体系.在实验的基础上,采用密度泛函理论(DFT)的B3LYP/Lanl2dz计算方法对2种配合物进行了几何优化、前线轨道能量、单点能量等后续计算.     

新型N-(2-氧乙酸-3-甲氧基)苄叉丙二胺合铜(Ⅱ)的合成、晶体结构及抑菌活性

将N,N′-二(2-氧乙酸-3-甲氧基)苄叉丙二胺(H2L1)与CuCl2的乙醇溶液混合,调pH=9,获得新型不对称的铜(Ⅱ)配合物Cu(Ⅱ)ClL2(L2=N-(2-氧乙酸-3-甲氧基)苄叉丙二胺)(1).采用元素分析、1H NMR和FTIR光谱等手段对H2L1和配合物1进行了结构表征,测定了配合物1的晶体结构.结果表明:晶体属于三斜晶系,空间群为P墿;晶胞参数a=0.7990(3)nm,b=0.8290(3)nm,c=1.0704(4)nm,α=87.676(4)°,β=73.034(4)°,γ=85.987(5)°,V=0.6764(4)nm3,Z=2,F(000)=358,Dc=1.720g/cm3,μ=1.826mm-1,R1=0.0344,wR2=0.0995.在配合物1中,Cu原子均为五配位,构成扭曲四方锥构型.并初步研究了配合物1抑菌活性.     

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.     

An Analysis of Catherine＇s Character——Wuthering Heights

Wuthering Heights, Emily Bronte＇s only novel, was published in December of 1847 under the pseudonym Ellis Bell. The book did not gain immediate success, but it is now thought one of the finest novels in the English language. Catherine is the key character of this masterpiece, because everybody and everything center on her though she had a short life. We can understand this masterpiece better if we know Catherine well.     

Lower Paleozoic oil relationships within Williston Basin, Canada

The Williston Basin is a significant petroleum province, containing oil production zones that include the Middle Cambrian to Lower Ordovician, Upper Ordovician, Middle Devonian, Upper Devonian and Mississippian and within the Jurassic and Cretaceous. The oils of the Williston Basin exhibit a wide range of geochemical characteristics defined as "oil families", although the geochemical signature of the Cambrian Deadwood Formation and Lower Ordovician Winnipeg reservoired oils does not match any "oil family". Despite their close stratigraphic proximity, it is evident that the oils of the Lower Palaeozoic within the Williston Basin are distinct. This suggests the presence of a new "oil family" within the Williston Basin. Diagnostic geochemical signatures occur in the gasoline range chromatograms, within saturate fraction gas chromatograms and biomarker fingerprints. However, some of the established criteria and cross-plots that are currently used to segregate oils into distinct genetic families within the basin do not always meet with success, particularly when applied to the Lower Palaeozoic oils of the Deadwood and Winnipeg Formation.     

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.     

Design and analysis of generic LBS application developing platform

Location based services is promising due to its novel working style and contents.A software platform is proposed to provide application programs of typical location based services and support new applications developing efficiently. The analysis shows that this scheme is easy implemented, low cost and adapt to all kinds of mobile nework system.     

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