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951.
952.
953.
Xiaoqing Zeng Helmut Beckers Helge Willner Raphael J. F. Berger Stuart A. Hayes Norbert W. Mitzel 《ChemInform》2011,42(19):no-no
The title compound is characterized by IR (gas phase, Ar matrix), Raman (liquid, amorphous, and crystalline solid), and 19F, 31P, 14N and 15N NMR spectroscopy, as well as by quantum chemical DFT calculations. 相似文献
954.
Yanli Zeng Xiaoyan Li Xueying Zhang Lingpeng Meng Prof. Dr. Shijun Zheng 《中国化学》2010,28(12):2345-2352
MP2/aug‐cc‐pVDZ calculations are carried out on the geometries, vibrational frequencies, interaction energies and topological properties for the π‐type halogen‐bonded complexes between propargyl radical and dihalogen molecules ClF, BrF and BrCl. There are two kinds of geometries: complex ( a ) involves the interaction between the X (X=Cl, Br) atom and the midpoint of C(1) –C(2) bond, complex ( b ) involves the interaction between the X atom and C(3) atom. The lengths of the halogen bond, the frequencies of the halogen bond, the elongation extent of the X–Y (XY=ClF, BrF, BrCl) bond, topological parameters at the BCPs of the halogen bond and X–Y bond are all well consistent with the interaction energies. The interaction of complex ( a ) is stronger than that of complex ( b ); the interaction of propargyl···BrF is stronger than that of propargyl···ClF and propargyl···BrCl. For the complexes ( a ) and ( b ), the charge transfer is observed from propargyl radical to XY, the atomic energy, the dipolar polarization, and the volume of the halogen atom X decrease upon complex formation. 相似文献
955.
956.
Cheng-Hui Zeng Yun-Jun Liu Zheng-Zheng Li Zhen-Hua Liang Hong-Liang Huang Fu-Hai Wu 《Transition Metal Chemistry》2010,35(6):731-736
Two new ruthenium(II) polypyridyl complexes, [Ru(dmp)2(maip)](ClO4)2
1 (maip = 2-(3-aminophenyl)imizado[4,5-f][1,10]phenanthroline and [Ru(dmp)2(paip)](ClO4)2
2 (paip = 2-(4-aminophenyl)imidazo[4,5-f][1,10]phenanthroline, dmp = 2, 9-dimethyl-1,10-phenanthroline) have been synthesized and characterized.
The DNA-binding behaviors of complexes 1 and 2 were studied by viscosity measurements, thermal denaturation, and absorption titration. The results show that the two complexes
intercalate between the base pairs of DNA. The DNA-binding constants K
b for complexes 1 and 2 were determined to be 3.23 ± 0.16 × 104 M−1 (s = 0.97) and 4.34 ± 0.65 × 104 M−1 (s = 1.13). The cytotoxicity of these complexes has been evaluated by MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium
bromide) assay. The IC50 values are 35.70, 41.04, 55.25 and 37.50 for complex 1 and 37.02, 103.08, 130.07 and 37.80 for complex 2 against BEL-7402, C-6, HepG-2 and MCF-7 cell lines, respectively. The antioxidant activity against hydroxyl radical (OH•)
was also investigated. 相似文献
957.
金属铜配合物催化氧化1-(3,4-二甲氧基苯)乙醇的动力学研究 总被引:3,自引:0,他引:3
合成了1-(3,4-二甲氧基苯)乙醇(DMPE)作为木质素模型物,并用初始速率法研究了40℃时在pH6.5~8.5磷酸缓冲溶液中N,N-双(2-乙基-5-甲基-咪唑-4-亚甲基)乙醇胺合铜、N,N-双(2-(2-羟乙基胺基)乙基)草酰胺合铜和5,7,12,14-四甲基-1,4,8,11-四氮杂环十四-4,7,11,14-四烯合铜催化氧化1-(3,4-二甲氧基苯)乙醇的动力学,提出了1-(3,4-二甲氧基苯)乙醇氧化反应动力学模型,并由此计算出不同pH值条件下催化反应动力学参数k2和Km.铜配合物的催化活性随着pH的增大而增大.具有大共轭体系的配体催化剂表现出更好的催化活性.提出并讨论了H2O2氧化DMPE的催化氧化反应机理. 相似文献
958.
采用量子化学的密度泛函B3LYP和二阶微扰MP2(full)方法对C4H4Y(Y=O,S,Se)与BX3(X=H,F,Cl)形成的电子授受型复合物进行了研究,所得18个复合物的构型包括BX3位于C=C双键上方的π-p作用型和B与O,S,Se直接作用的n-p作用型.体系C4H4Y-BH3以n-p作用型较为稳定,体系C4H4Y-BF3,C4H4Y-BCl3的π-p和n-p作用型复合物稳定性相当.对各复合物的几何构型、振动频率和自然键轨道分析表明,复合物的形成过程中均存在几何构型的改变、电荷的转移和振动频率的变化,它们的变化规律与复合物稳定性的变化规律基本一致,即按H,F,Cl的顺序依次降低. 相似文献
959.
960.
Zhanghua Zeng Dr. Angel A. J. Torriero Dr. Alan M. Bond Prof. Leone Spiccia Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(30):9154-9163
The [Fc? bis{ZnII(TACN)(Py)}] complex, comprising two ZnII(TACN) ligands (Fc=ferrocene; Py=pyrene; TACN=1,4,7‐triazacyclononane) bearing fluorescent pyrene chromophores linked by an electrochemically active ferrocene molecule has been synthesised in high yield through a multistep procedure. In the absence of the polyphosphate guest molecules, very weak excimer emission was observed, indicating that the two pyrene‐bearing ZnII(TACN) units are arranged in a trans‐like configuration with respect to the ferrocene bridging unit. Binding of a variety of polyphosphate anionic guests (PPi and nucleotides di‐ and triphosphate) promotes the interaction between pyrene units and results in an enhancement in excimer emission. Investigations of phosphate binding by 31P NMR spectroscopy, fluorescence and electrochemical techniques confirmed a 1:1 stoichiometry for the binding of PPi and nucleotide polyphosphate anions to the bis(ZnII(TACN)) moiety of [Fc? bis{ZnII(TACN)(Py)}] and indicated that binding induces a trans to cis configuration rearrangement of the bis(ZnII(TACN)) complexes that is responsible for the enhancement of the pyrene excimer emission. Pyrophosphate was concluded to have the strongest affinity to [Fc? bis{ZnII(TACN)(Py)}] among the anions tested based on a six‐fold fluorescence enhancement and 0.1 V negative shift in the potential of the ferrocene/ferrocenium couple. The binding constant for a variety of polyphosphate anions was determined from the change in the intensity of pyrene excimer emission with polyphosphate concentration, measured at 475 nm in CH3CN/Tris‐HCl (1:9) buffer solution (10.0 mM , pH 7.4). These measurements confirmed that pyrophosphate binds more strongly (Kb=(4.45±0.41)×106 M ?1) than the other nucleotide di‐ and triphosphates (Kb=1–50×105 M ?1) tested. 相似文献