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Mn-complexes in which Mn atom ligand with the N atom within ligand can stimulate the recovery of electron transfer and oxygen evolution. The trinuclear Mn-complex is extremely sensitive to the addition of CaCl2. It is suggested that there is an interaction between Ca2 and carboxyl within the trinuclear Mn-complex during photoactivation and this interaction benefits the ligation of Mn atom to the apo-WOC and form an active WOC. Binuclear MnMn complex shows slightly higher efficiency than binuclear MnMn complex in restoration of O2 evolution activity. It is suggested from our results that recovery of electron transport and O2 evolution with synthetic Mn-complexes is affected by different factors. Cl- can stimulate the reconstitution of WOC at the concentration of over 100mM;the maximal recovery of O2 evolution activity requires the presence of CaCl2 and 33 kDa protein polypeptide together. Bicarbonate can stimulate the reconstitution of WOC.

锰配合物中锰原子与配体中的氮原子配位连接时,能显著恢复电子传递活性和放氧活性;三核锰化合物在重组时对CaCl2的存在非常敏感,我们认为Ca2 与三核锰化合物中的羧基之间存在一定的相互作用,而这种作用有助于锰原子的光配位进而使三核锰化合物易于组装成有活性的水氧化复合物:双核锰化合物MnMn比双核锰化合物MnMn在恢复放氧活性方面更有效;影响锰化合物电子传递能力恢复的因素与影响锰化合物放氧活性恢复的因素不同;在锰蔟重组过程中,氯离子的浓度必须在100mM以上,才能有效进行光重组;最大光重组效率的获得必须有钙离子和33kDa多肽同时存在;碳酸氢根离子促进锰化合物与去锰光系统II的光组装。

In complex 1,Cucan be described as a four-coordinated square planar geometry.Compound 8 is the sodium salt of plumbagin and exists as ionic compound.Compounds 9-16 are the rare earth complexes of plumbagin with La,Y,Dy,Sm,Gd,Nd,Erand Eu.Compound 17 is binuclear Y complex.18 is mononuclear Ycomplex with plumbagin and another ligand from Plumbago Zeylanica.Compounds 19-21 are the ternary complexes with plumbagin and 2,2\'-bpy and phen as assistant ligand.In 19, the geometry of Cucan be described as five-coordinated distorted square pyramid that exists in a dimer through the weak bonding,and 1-D chain structure is formed by intermolecular hydrogen bonds.

化合物1的单晶结构分析表明1具有四配位平面四边形结构,化合物8是白花丹素的Na盐,以离子化合物形式存在;化合物9~16为白花丹素的La,Y,Dy,Sm,Gd,Nd,Er,Eu的稀土金属配合物;化合物17是白花丹素的双核钇结构;化合物18为白花丹素的单核钇结构,该配合物除了含白花丹素外,还有来自白花丹植物中的另一个单体化合物也参与配位;化合物19~21是以2,2\'-联吡啶和邻菲咯啉等含N配体为辅助配体,具有白花丹素—含N配体—金属离子的三元配合物,化合物19是白花丹素和2,2\'-联吡啶与Cu的配合物,具有五配位的四方锥构型,通过Cu…O弱的成键作用形成二聚体,再通过分子间的氢键作用进一步形成一维链状结构,化合物20和化合物21是白花丹素分别与2,2\'-联吡啶和邻菲咯啉的Zn配合物,都具有六配位八面体构型的双核锌配合物,呈一维链状结构,化合物20中链与链之间的大量氢键将一维链扩展成二维层,分子间的π-π堆积作用进一步形成三维结构。

In the aluminum solution ,the trivalence aluminum ion combi...

另一方面,在这种铝盐溶液中,三价铝离子是以铝水配合物的形态存在,配位水发生水解生成羟基配离子,其通过羟基桥联结,放出水分子,并逐级由单体配合成双核、三核以致形成多核羟基配合物。

In the aluminum solution ,the trivalence aluminum ion combines with water to form the coordination compound and then the coordination waters hydrolyze into hydroxide ions. The hydroxide ions can join up each other by the hydroxide ion bridges so that the double cores, three cores and multiple cores coordination compounds are formed.

另一方面,在这种铝盐溶液中,三价铝离子是以铝水配合物的形态存在,配位水发生水解生成羟基配离子,其通过羟基桥联结,放出水分子,并逐级由单体配合成双核、三核以致形成多核羟基配合物。

The synthesis and characterization of asymmetric dinuclear and mononuclear vanadium complexes show that the pH value is very important for the products\' formation and isolation. In some pH range, theα-alkoxy bridge was easy to break and form asymmetric dinuclear and mononuclear vanadium structure.

三、不对称的双核钒和单核钒配合物的合成和表征显示,pH值对产物的形成和分离具有至关重要的作用。pH值在一定范围内,柠檬酸的烷氧基氧作为桥氧的化学键才容易断开,从而形成不对称的双核钒和单核钒结构。pH值不仅影响不对称双核V_2O_3钒配合物和单核钒配合物的形成,还关系到钒还原的速度。

In this thesis, a series of complexes based on aromatic multicarboxylic acids have been successfully synthesized in solutions or under hydrothermal conditions. Their structure and properties are investigated.(1) Eight complex compounds have been synthesized and characterized by X-ray single crystal diffractive technology: The eight complexes are listed as following: [Cu242] complex 1 [Cd22(H2O)4]·4H2O complex 2 [Co(H2btc)(H2O)3] complex 3 [Co2(H2O)2]·H2O complex 4 [Ni22(H2O)4] complex 5 [Cu22(H2O)4] complex 6 [Co(H2biim)2(H2O)2](H2btc) complex 7 [Zn(H2biim)2(H2O)2](H2btc) complex 8 The structure of complex 1 is dinuclear complex resulted from weak interactions(0-D chain); complex 2 is 1-D chain stucture result from interactions of water molecules; complex 3、4、5、6 are coordination polymers using hydrothermal synthses, where the first kind ligand is H4btc, the second kind ligand is phen and Co2+、Ni2+、Cu2+ as center ions, respectively. While the coordination enviroment of Co2+ is the same in complex 3, the coordination geometries around the Co atoms in complex 4 are obviously different because of the different reaction conditions. In complex 4, the 1-D chains are connected into 2-D layer through carboxy groups of ligand H4btc. The structures of complex 5、6 are 1-D chain stucture result from interactions of carboxy groups in ligand H4btc. Complex 7、8 are homeomorphy compounds. Either of them are linked to the 3-D chains through intermolecular hydrogen bonds. Each H4btc lose two protons and H2btc2- acts as negative electron balance.

合成了8个结构新颖的配合物,并用X-射线单晶结构分析方法确定了晶体结构,分别为: [Cu242] 配合物1 [Cd22(H2O)4]·4H2O 配合物2 [Co(H2btc)(H2O)3] 配合物3 [Co2(H2O)2]·H2O 配合物4 [Ni22(H2O)4] 配合物5 [Cu22(H2O)4] 配合物6 [Co(H2biim)2(H2O)2](H2btc)配合物7 [Zn(H2biim)2(H2O)2](H2btc)配合物8 配合物1是一个依靠弱作用连接的双核铜结构;配合物2借助水分子形成一维链状结构;配合物3、4、5、6是以H4btc为第一配体、phen为第二配体,通过水热法合成的配合物,其中,Co2+、Ni2+、Cu2+为中心离子;配合物3中的二价钴离子具有相同的配位环境,不同反应条件下得到的配合物4中的二价钴离子存在不同的配位环境,在配合物4中,一维链通过H4btc上的羧基形成一个二维层结构;配合物5、6是借助H4btc上的羧基形成的一维链状结构;配合物7、8属于异质同晶结构,它们的分子通过分子间氢键形成三维网状结构,H4btc上的羧基失去2个质子,作为一个二价负离子起到电荷平衡作用。

Two new binuclear complexes, [TpCu(μ-1, 1-N3)2CuTp](1) and [Tp(superscript *)Co2CoTp(superscript *)](2) Tp=tri (pyrazolyl borate and Tp(superscript *)=3,5-dimethyltri borate, have been synthesized and characterized by IR, UV-vis, ESR, and CV. The crystal structures of both complexes have been determined by X-ray single crystal diffraction.

合成了两个新型的含三吡唑硼配体的双核铜配合物[TpCu(μ-1, 1-N3)2CuTp](1)和双核钴配合物[TpCo2CoTp](2),并通过IR,UV-vis,EPR,CV,X-射线单晶衍射等手段进行表征。

In order to get the information of interaction between metal complex and DNA and select metal complexes which can cleave DNA effectively, twenty seven transition metal complexes containing O/N coordinate atoms have been synthesized in this thesis. We report the synthesis, crystal structure and properties of the complexes. One of the complexes is the first μ〓-oxalato tetranuclear Cu complex, in which there is ferromagnetic interaction between the copper atoms bridged by oxalate ions. Two trinuclear copper complexes containing partial cubane Cu〓O〓 cores have been synthesized and discussed the magnetic properties.

为了解金属配合物与DNA的相互作用及筛选能有效切割DNA的金属配合物,为无机药物合成及应用提供基础信息,本文利用十个含N、O原子的多齿配体设计合成了二十七个未见文献报道的过渡金属配合物,并解析了它们的晶体结构:其中包括首例μ〓-草酸根的四核铜配合物;合成了两个具有μ〓-OH〓三核缺角立方烷结构的Cu配合物;以HCBP衍生物为配体合成了七个过渡金属配合物;以SCN〓、N〓,C〓O〓等为桥联配体,以dmpyen为端基配体合成了十一个配合物。

All the ligands and complexes have been characterized with ~1H-NMR, MS and EA.X-Ray single crystal diffraction reveals that zirconium complex containing the tert-butyl substituted N_2O_2 ligand is an oxo- and hydroxyl-bridged dinuclear structure, which is possibly formed by partial hydrolysis of chlorides at one of the zirconium centers. A tetranuclear zirconium complex has been obtained and chacaterized, which is formed by complete hydrolysis of the chlorides at the zirconium centers.

通过研究配合物的单晶结构,我们发现叔丁基取代的不对称N_2O_2配体与ZrCl_4反应生成的锆配合物为氧桥和羟基桥连接的双核锆配合物,中间过程涉及单核锆配合物中氯原子部分水解,并得到氯原子部分水解的双核锆配合物和全部水(来源:8e6eAB67C论文网www.abclunwen.com)解的四核锆配合物的晶体结构,在晶体培养过程中发现双核锆配合物能够以手性自发拆分结晶析出。

Both were measured using X-ray single crystal diffraction. For the crystal in MeOH, X-ray in compound. In an ansymmetry unit, there are two Cu atoms, two ligands and twosolvent methanol molecules. The tetranuclear complex contains two kinds of Cucenter.

本文在MeOH中得到了阶梯型四核铜骨架配合物;在THF中得到了扭曲的立方烷型四核铜骨架配合物,经晶体结构分析表明,阶梯型四核铜骨架配合物是由两个Cu2被μ~3-剪刀撑二个醇羟基O所连接形成中心对称的二铜二聚体结构。

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