Reaction of Tetracopper(I)-Phosphonitocavitand with PhSeSiMe3: Synthesis and Structure of a Polyanionic Cluster [pyH]6[(CuCl)9(μ3-SePh)5(μ4-SePh)]

Treatment of tetracopper(I)-phosphonitocavitand [1·Cu₄(μ-Cl)₄(μ₄-Cl)] (2) (1 = tetraphosphonitocavitand [rccc-2,8,14,20-tetrakis-(iso-butyl)-phosphonitocavitand (C₄₄H₄₈O₈P₄Ph₄)]) with PhSeSiMe₃ in THF at low temperature afforded a novel polyanionic cluster [pyH]₆[(CuCl)₉(μ₃-SePh)₅(μ₄-SePh)] (4) as a major product along with a new tetracopper(I)-phosphonitocavitand (3) with a centered μ₃-Cl. Molecular structure of anionic cluster in 4 consists of six PhSe⁻ bridging ligands containing five μ₃-SePh and one exceptional μ₄-SePh bridging nine copper atoms, of which eight copper atoms have trigonal coordination geometry and the other has distorted tetrahedral geometry. Dedicated to Professor Han-Qin Liu on the occasion of his 70th birthday.     

Chemical Reactions and Kinetics of the Carbon Monoxide Coupling in the Presence of

The chemical reactions and kinetics of the catalytic coupling reaction of carbon monoxide to diethyl oxalate were studied in the presence of hydrogen over a supported palladium catalyst in the gaseous phase at the typical coupling reaction conditions. The experiments were performed in a continuous flow fixed-bed reactor. The results indicated that hydrogen only reacts with ethyl nitrite to form ethanol, and kinetic studies revealed that the rate-determining step is the surface reaction of adsorbed hydrogen and the ethoxy radical (EtO-). A kinetic model is proposed and a comparison of the observed and calculated conversions showed that the rate expressions are of rather high confidence.     

A bifunctional platinum(II) complex capable of intercalation and hydrogen-bonding interactions with DNA: binding studies and cytotoxicity

The interactions of [Pt(CNN)(4-dpt)]PF(6), (1; 4-dpt=2,4-diamino-6-(4-pyridyl)-1,3,5-triazine, HCNN=6-phenyl-2,2'-bipyridine) with double-stranded DNA, poly(dA-dT)(2), and poly(dG-dC)(2) were examined by spectroscopic, electrophoretic, and hydrodynamic methods. The spectroscopic data were analyzed with McGhee, van't Hoff, and Gibbs-Helmholtz equations. In a comparative study, [Pt(CNN)(py)]PF(6) (2; py=pyridine) was prepared and the nature of its binding towards DNA was investigated [preliminary results: ChemBioChem 2003, 4, 62-68]. For reactions with calf thymus DNA at 20 degrees C, the intrinsic binding constants for 1 and 2 are (4.6+/-0.2)x10(5) and (2.3+/-0.3)x10(4) mol(-1) dm(3), respectively. Results of DNA-binding reactions revealed that 1 and 2 preferentially bind to the AT sequence of duplex DNA. Intercalation is the preferred binding mode for 2, whereas both intercalation and minor-groove binding are observed for 1. Complex 1 is cytotoxic against a number of carcinoma cell lines, including KB-3-1, CNE-3, and HepG2, and remains potent against multidrug- or cisplatin-resistant KB-V-1 and CNE1 cell lines, for which the resistance ratios are 1.6 and 1.5, respectively. Importantly, 1 is almost an order of magnitude less toxic to the normal cell line CCD-19Lu (IC(50)=176+/-1.7 microM) and it selectively induced apoptosis leading to cancer cell death with less than 5 % detectable necrosis.     

化学教科书评价指标体系的制定

化学教科书在学校教育中起着重要的作用．客观地、有效地、可操作性地评价化学教科书，对促进化学教科书质量的提高和教科书的多样化有着重要的意义．基于对化学教科书概念的界定、化学教科书的结构以及功能三个方面的分析。提出了构建化学教科书的评价指标体系．     

用MATLAB编程求解Zn(Ⅱ)-NH4Cl-NH3-H2O体系热力学模型

应用MATALAB语言编写程序建立Zn(Ⅱ)-NH4Cl-NH3-H2O体系的多元非线性热力学模型并求解其热力学关系. 模型中共有pH值、游离氨浓度、总氨浓度、溶液中总锌浓度、总氯浓度和游离氯离子浓度 6个变量, 共有锌量、氨量、氯量和电荷平衡4个方程. 根据电算指数法, 模型中各离子浓度之间服从对数和指数关系. 输入需求解的方程及其边界条件, 求出总氨浓度和总氯浓度分别在0～10 mol/L范围内变化时, 其他未知数随之变化的关系, 并绘制各种重要的热力学关系图, 包括各种立体图和二维图. 对用MATLAB求解模型和用BASIC求解模型的所得结果以及与氧化锌溶解度实验所得结果之间的差异进行分析. 结果表明, 用MATLAB编程求解冶金多元非线性热力学模型, 过程简单, 所得结果精确可靠, 根据计算所得数值可方便地绘制成各种图形, 便于进行冶金分析.     

改进无机化学实验

探讨了改进无机化学实验的方法,特别对无机化学实验的微型化、绿色化、开放化、综合化等方面进行了讨论,为提高实验教学质量、培养高素质人才提出了改革方案.     

新型Cu(II)双核配合物的合成、结构表征和量化计算

以二(2-苯并咪唑亚甲基)胺(N3)为配体,合成了一种新型Cu(II)双核配合物作为超氧化物歧化酶(SOD)的模型化合物.采用元素分析、UV和IR光谱进行了表征,应用X射线衍射方法测定了晶体结构,并利用G98W程序在HF/LANL2DZ基组水平上对该双核配合物进行了量子化学计算.晶体结构分析表明,Cu(II)双核配合物的化学式量分子(C42H40N12O17Cl4Cu2)是以4,4′-联吡啶为桥的Cu(II)双核配合物单元,Cu(II)与配位原子形成变形八面体构型,轴向配位氧原子来源于高氯酸根.量化计算所得原子轨道贡献和原子净电荷布居分析结果与晶体结构中的配位情况相符.     

苯及其氮取代体系的电子结构和性质比较

采用量子化学计算方法讨论了苯及其吡啶、哒嗪、嘧啶、吡嗪 5个分子的几何构型、稳定性和前线分子轨道。得到氮取代使前线分子轨道组成发生变化 ,轨道能级差减小 ,反应活性增加的结果。     

含钡钙矾石相的量子化学研究

钙矾石是水泥的主要水化产物之一，含钡钙矾石相是新水泥矿物含钡硫铝酸钙的主要水化产物，它们是水泥石强度的主要来源。本文利用新发展起来的量子化学ＳＣＣ—ＤＶ—Ｘａ方法对钙矾石相和含钡钙矾石相进行了研究，获得了分子结构的键级、集居数、净电行和共价键级等数据。结果表明：两矿物结构中Ａｌ—Ｏ键的化学参数变化不大，差异较大的是钙矾石中Ｃａ—Ｏ键和含钡钙矾石中Ｂａ—Ｏ键的键级和共价键级。认为Ｂａ—Ｏ键的键级和共价键级大于Ｃａ－Ｏ键是含钡硫铝酸钙水化强度大于硫铝酸钙的主要原因之一。