离子键

The peroxy bond of dihydroartemisininis essential for it\'s antimalarial and antitumor activity. In order to understand the mechanism of antimalarial and antitumor, electrochemical method were used to study the interaction between DHA with Cu ion and Bi ion.

双氢青蒿素中的过氧键是抗疟、抗肿瘤的关键活性部位，为了探讨金属离子对DHA中过氧键的影响，本文采用电化学方法研究了Cu、Bi对DHA的作用，并探讨了其作用机理。

The compound is an ionic compound consisting of a cation NH(subscript 4 superscript +) and an anion C6H2N3O(subscript 9 superscript -), and it is the mono-substituted salt of TNPG. Since the existence of complicated hydrogen bond networks and electrostatic attraction between NH(subscript 4 superscript +) cation and C6H2N3O(subscript 9 superscript -) canion, the compound possesses better stability and low sensitivity.

该化合物是由一个铵根离子与一个一价的三硝基均苯三酚负离子相结合而形成的离子型化合物，分子中存在的大量氢键及铵根离子与三硝基均苯三酚负离子之间的静电引力使得该化合物具有较高的热稳定性和较低的感度。

Halogen ion can enter and break the phosphate glass network when they exceed certain content. The short range structure of metaphosphate and polyphosphate glasses are all built with phosphate chains. Most of lead ions still act as network modifiers, and some lead ions enter glass network to form tetrahedron or Pb-O-P linear linkages.

Br〓和F〓离子达到一定浓度时就会进入网络，使得玻璃网络发生断裂。P〓O〓含量为50mol％和40mo1％的玻璃样品结构都为链状结构，一部分pb〓离子进入玻璃网络中作为网络形成体，形成四面体或Pb-O-P键：而大部分的pb〓离子仍然作为网络修饰本。

It is the fluorosilicic ion that exsits in the slurry and plays an important role in flotation, fluorosilicic ion not only reacted with Fe〓 on the surface of aegirine to form ionic compound, but also formed stable Si-F bond in Si-O etching reaction. Only ionic compound was obtained when it was attached to hematite surface according to the theories of coordination chemistry, Compared with SiF〓, Fatty acid ion preferentially acts with Fe〓 on the minerals surface, therefore, SiF〓 Can't obstruct the adsorption of collector on the surface of hematite completly, but can reduce the flotation recovery of aegirine selectively.

运用FTIR、XPS等测试方法仔细研究了氟硅酸盐抑制剂对含铁硅酸盐钠辉石的选择性抑制作用机理，氟硅酸盐在弱酸性条件下对赤铁矿浮选的抑制作用很微弱，而对含铁硅酸盐钠辉石强烈抑制，从而扩大了两者之间的浮选差异；SiF〓是矿浆中起抑制作用的主要成分，SiF〓不仅与钠辉石表面的Fe〓形成离子型配合物，而且还与Si-O键形成稳定的Si-F共价键，而与赤铁矿表面只能形成离子型配合物，根据晶体配位场理论，与SiF〓相比较羧酸根离子将优先与矿物表面Fe〓发生配位作用，因此SiF〓的存在并不能完全阻碍捕收剂在赤铁矿表面的吸附作用，却能够选择性地抑制钠辉石的上浮。

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。

The results of the present research are as follows, The correlation between physico-chemical properties of organic compounds and their competitive power was studied, and it was indicated that organic compounds preferable to form H-bonding with organic matter of sorbents have stronger competitive power; Sorption behaviors of ionizable organic compounds in different species and their competitive power were examined, and the results showed that phenols and carbonxylic acids with benzyl circle have much stronger competitive power in molecular species than in ionized species, because negative charges of anionic forms can depressed their adsorption on the surface of the sediment; in contrast, organic bases such as aniline and p-chloroaniline show weaker competitive power in molecular species than in ionized species, and this is because both species of the organic bases could adsorb strongly onto the sediment; there is a correlation between competitive power of organic pollutants in multi-solute systems and their sorption isotherm nonlinearity in single-solute systems, and organic compounds whose sorption isotherms is linear in single-solute systems hardly have competitive power in multi-solute systems; Competitive sorption effects in more than two-solutes systems was studied, and it was exhibited that mixture of two cosolutes each of which could suppress sorption of nominal solute onto the sediment had synergistically competitive sorption effect on the nominal solute; A method about incorporating sorption/desorption of organic pollutants into river water quality model was developed, and discussion about degree of sorption/desorption effect on model prediction for different organic compounds was made, which will provide theoretical basis and practical processes for setting up more accurate water quality model.

论文主要取得了以下研究成果。(1)有机化合物的吸附竞争能力与其物化性质具有相关性，易与沉积物有机质形成氢键的化合物其竞争能力也比较强；(2)可离子化有机化合物的吸附竞争能力与其存在形态有关。酚类、含苯环的羧酸类化合物，其离子态的吸附竞争能力远小于分子态，其机理为有机酸阴离子所带的负电荷抑制了表面吸附能力，主要发生分配作用；而苯胺类化合物，其离子态和分子态都表现出显著的竞争能力，而且离子态的竞争能力略强于分子态，原因在于有机碱阳离子所带的正电荷促进了其表面吸附能力；有机化合物竞争能力的强弱与其单组分吸附等温线的非线性程度具有一定的相关性，吸附等温线近似为线性的化合物没有或只具有微弱的竞争能力；(3)对目标有机化合物的吸附具有竞争效应的有机化合物混合后，将对目标有机化合物的吸附产生协同竞争效应；(4)以京杭运河为例，率先提出了将有机污染物的吸附／脱附作用及水文水力参数耦合到水质模型中的方法，并讨论了吸附／脱附作用对不同有机污染物预测模型的影响，为建立更准确的水质模型及进行更客观的风险和生态评估提供了参考依据。

It was found that the central metal ion is located at the symmetric center of the molecule. Four oxygen atoms from two H2O molecules and two 〔C6H4(CO2)2〕2- groups are coordinated with copper ion to form a similar planar square coordination configuration. There is one only unidentate coordination bond between O(1) in 〔C6H4(CO2)2〕2- and Cu2+.

结构分析发现，中心金属离子位于分子的对称中心位置，铜离子与来自2个水分子和2个邻苯二甲酸根中的4个氧原子形成近似正方形平面配位，邻苯二甲酸根是以1个O(1)与Cu2+离子形成单齿配体，O(2)和Cu2+之间没有形成配位键。

Comparing with the result of methyl iodide in intense laser field, some differences are observed:(1) at the same laser field intensity, the highest charged fragment ion of methyl bromide was Br(superscript 3+), lower than I(superscript 6+) of methyl iodide;(2) the dehydrogenation channel was observed in the multiphoton dissociation or Coulomb explosion of methyl bromide, but was not observed in the case of methyl iodide;(3) HBr(superscript +) was observed, but there was no similar channel in the case of methyl iodide;(4) for methyl bromide, the valid charge distance of Coulomb explosion increases with the product of p and q; while in the case of methyl iodide, the distance remained almost the same;(5) the producing channel of CH(superscript + subscript m)(m=0, 1, 2) is different from the ionization-dissociation of methyl iodide in which the stepwise dissociation of CH3(superscript +) was thought to be the main channel, CH(superscript + subscript m)(m=0, 1, 2) of methyl bromide are mainly from the products of the direct dissociation of the dehydrogenated parent ions instead of the stepwise dissociation of CH3(superscript +).

与碘甲烷在强场中的实验结果对比发现：(1)在相同的激光场强下，碘甲烷电离解离的最高价碎片离子为I(上标 6+)而溴甲烷为Br(上标 3+)；(2)溴甲烷质谱中存在母体离子的脱氢产物CHBr和CHBr(上标 2+)，而对于碘甲烷，没有检测到这些通道，C-I键首先断开；(3)质谱中存在H^79Br和H^81Br，而碘甲烷的电离解离中不存在HI产物；(4)溴甲烷库仑两体爆炸的有效电荷间距随着两碎片电荷乘积的增大而增大，而对于碘甲烷此间距几乎不随电荷乘积变化；(5)CH(m=0， 1， 2)的主要生成通道可能与碘甲烷不同，不是来自CH3的顺序脱氢，而是来自脱氢母体离子的直接解离。

We note from the further studies that in the crystals, which sharing the similar crystal structures and coordinational environments, the magnitude of the Stokes shift of the luminescence of the dopant ion is in line with the average covalency of the replaced lattice site. This is because that the nature of Stokes shift is the energy transfer from the luminescent ion to the host lattice. The value of this energy is determined by the frequency of the host lattice in which the frequency is controlled by the chemical bond characters.

更深入的研究发现，在晶体结构和中心离子配位环境非常相似的系列晶体中，掺杂离子发射光的Stokes位移值与其所取代格位的平均共价性成正比的关系，这是由于Stokes位移的本质是发光离子在发光过程中向基质以光波辐射的形式传递能量，这一能量的大小是由基质的振动频率决定的，而基质的化学键性质恰恰决定着基质的振动频率。

A large releases of kinetic energy for channel CH3CS++ H of least energy might result from a dissociation mechanism according to which c-C2H4S+ isomerizes to a local minimum CH3CSH+ and then dissociates through a transition state to form CH3CS++ H. On the other hand, a predicted dissociation energy 11.05 eV for c-C2H4S ?

实验中观察到环硫乙烯离子解离成CH3CS++ H的解离通道释放出大量的平均动能，并采用G3计算预测环硫乙烯离子的解离通道，推测环硫乙烯离子异构化至次稳定态CH3CSH+结构，再经过渡态结构，断裂S-H键生成C2H3S+和H，同时释放出大量的动能。

The split between the two groups can hardly be papered over.

这两个团体间的分歧难以掩饰。

This approach not only encourages a greater number of responses, but minimizes the likelihood of stale groupthink.

这种做法不仅鼓励了更多的反应，而且减少跟风的可能性。