还原席夫碱型三角架式金属配合物的合成和性质研究

由2，2，′，2＂-三氨基三乙胺(tren)与N-氧化吡啶醛经席夫碱型缩合，然后还原C=N双键形成的产物为配体(L¹)，合成了一系列新三角架式过渡金属配合物：［ML¹］²⁺［M=Mn(Ⅱ)、Ni(Ⅱ)和Zn(Ⅱ)］。利用元素分析、红外光谱、电子光谱和室温磁化率对配合物的结构和性质进行了研究。     

FIA-ICP/AES法分析茶叶浸取液中多元素的形态

本文报道了分析茶叶浸取液中[Zn、Mn、Fe、Al及Mg]形态的新方法。研究了以C-18柱为分离柱的流动注射与ICP/AES的联用技术。     

双(N 氧化吡啶 2-甲醛)缩1,2-丙二胺镍配合物的合成和晶体结构

合成所得双(N-氧化吡啶-2-甲醛)缩1,2-丙二胺的镍(II)配合物[Ni(piopn)(H_2O)_2](ClO_4)_2的晶体属空间群C_s~4-C_c, 晶胞参数a=0.7397(3) nm, b=1.3187(7) nm, c=2.5502(14) nm, β=102.18(4)°. 用分子轨道理论的近似方法分析了该配合物的电子结构和分子轨道, 探讨了分子的结构特征与红外光谱的关系.     

Synthesis, characterization, photoluminescence and electroluminescence properties of new 1,3,4-oxadiazole-containing rhenium（I） complex Re（CO）3（Bphen）（PTOP）

A new 1,3,4-oxadiazole-contanining rhenium(I) complex,with the formula [Re(CO)_3(Bphen)(PTOP)],(Bphen=bathophe- nardine,PTOP=4-(5-p-tolyl-1,3,4-oxadiazd-2-yl)pyridine),is synthesized and characterized by elemental analysis,IR,~1H NMR, UV-vis and luminescence spectroscopy.The double-layer electroluminescence devices based on the Re(I) complex have been fabricated by spin-coating technique.The turn-on voltage,maximum efficiency,and brightness for green emission obtained from the devices are 9V,2.1cd/A and 165cd/m~2,respectively.     

Voltammetric Behavior of the Alizarin Red S Interaction with DNA and Damage to DNA

The electrochemical behavior and the interaction of alizarin red S (ARS) with calf thymus DNA was investigated on a bare glassy carbon electrode (GCE) and DNA modified GCE (DNA/GCE), respectively. ARS showed a pair of redox peaks at ?0.445 V and ?0.414 V on a bare GCE. On addition of DNA into the ARS solution, the peak current of ARS decreased and the peak potential positively shifted, but without new redox peaks appeared. The ARS reduction peak current increased with immersion time on a DNA/GCE. The results showed that ARS could interact with DNA molecules by intercalative binding mode. The equilibrium constant, binding number and the ratio of binding constant for oxidized and reduced ARS forms were obtained. The DNA damage was directly detected by appearance of guanosine and adenosine bases oxidation signal. The influence of experimental conditions on DNA damage extent was discussed in detail.     

硅酸及其盐的研究 XX聚硅酸溶液中的酸强度与分子结构的关系

本文利用无机酸系列的酸强度(pKa值)与羟基上氧原子的亲电子超离域度S(E)成线性关系的规律性,找出聚硅酸系列的相应线性方程为:并由此推测低聚硅酸溶液中可能存在的硅酸结构:在三聚硅酸溶液中主要存在着六元平面环的三聚体;在四聚硅酸中则主要存在着三种环状的四聚体。     

Evidence for orbital-specific electron transfer to oriented haloform molecules

Beams of hyperthermal K atoms cross beams of the oriented haloforms CF(3)H, CCl(3)H, and CBr(3)H, and transfer of an electron mainly produces K(+) and the X(-) halide ion which are detected in coincidence. As expected, the steric asymmetry of CCl(3)H and CBr(3)H is very small and the halogen end is more reactive. However, even though there are three potentially reactive centers on each molecule, the F(-) ion yield in CF(3)H is strongly dependent on orientation. At energies close to the threshold for ion-pair formation ( approximately 5.5 eV), H-end attack is more reactive to form F(-). As the energy is increased, the more productive end switches, and F-end attack dominates the reactivity. In CF(3)H near threshold the electron is apparently transferred to the sigma(CH) antibonding orbital, and small signals are observed from electrons and CF(3)(-) ions, indicating "activation" of this orbital. In CCl(3)H and CBr(3)H the steric asymmetry is very small, and signals from free electrons and CX(3)(-) ions are barely detectable, indicating that the sigma(CH) antibonding orbital is not activated. The electron is apparently transferred to the sigma(CX) orbital which is believed to be the LUMO. At very low energies the proximity of the incipient ions probably determines whether salt molecules or ions are formed.     

碳纳米管添加剂对质子交换膜燃料电池低铂载量膜电极性能的影响研究

以碳纳米管（CNT）作为低铂载量膜电极（CCM）催化层（0.1 mg_Pt·cm^-2）添加剂，研究了CNT的添加方式对催化层微观结构以及膜电极性能的影响.结果表明，与常规低铂载量催化层相比，在其表面喷涂一层CNT或将CNT均匀分散到Pt/C催化层中均有利于提升低铂载量膜电极的输出性能，在70℃和100%相对湿度条件下最高输出功率比常规低铂载量膜电极的0.522 W·cm^-2分别提升了22.4%和60.0%，并且均匀分散添加方式优于分层添加方式.其原因在于分层添加CNT后改善了低铂催化层和气体扩散层之间的接触界面，降低了催化层与扩散层间的接触电阻，而均匀分散添加方式除了可降低界面接触电阻外，还显著改善了低铂催化层中的气体传输，大幅提升了Pt催化剂的利用效率，使得膜电极电化学反应电阻明显降低.进一步对均匀分散添加方式中CNT的载量进行优化，表明CNT添加量为37.5 μg·cm^-2时电池输出性能最佳，70℃和100%相对湿度条件下的最大输出功率达到0.91 W·cm^-2.本研究工作表明，将CNT均匀分散添加到催化层中是一种有效提升低铂载量膜电极性能的方法.     

STM study on quinacridone derivative assemblies: modulation of the two-dimensional structure by coadsorption with dicarboxylic acids

We describe the two-dimensional (2D) assemblies of N,N'-dialkyl-substituted quinacridone derivatives on highly orientated pyrolytic graphite observed by scanning tunneling microscopy, and focus our discussion on whether the supramolecular organization can be modulated by the coadsorption of dicarboxylic acids. Our experiments have demonstrated that the quinacridone derivatives can form different 2D nanostructures when coadsorbed with dicarboxylic acids of different length at the liquid/graphite interface. Interestingly, N,N'-dihexadecyl-substituted quinacridone derivative alternately takes two different conformations in two columns for its coadsorption with pentadecanedioic acid and form a gridlike structure. It is shown that a cooperative effect of different interactions can be modulated by introducing guest molecule, leading to formation of different self-assembled nanostructures.     

Different catalysis role of in‐loop and out‐of‐loop waters in assisting HNS/HSN proton transfer isomerizations: Bridging vs. surrounding effect

In this work, a density function theory (DFT) study is presented for the HNS/HSN isomerization assisted by 1–4 water molecules on the singlet state potential energy surface (PES). Two modes are considered to model the catalytic effect of these water molecules: (i) water molecule(s) participate directly in forming a proton transfer loop with HNS/HSN species, and (ii) water molecules are out of loop (referred to as out‐of‐loop waters) to assist the proton transfer. In the first mode, for the monohydration mechanism, the heat of reaction is 21.55 kcal · mol^?1 at the B3LYP/6‐311++G** level. The corresponding forward/backward barrier lowerings are obtained as 24.41/24.32 kcal · mol^?1 compared with the no‐water‐assisting isomerization barrier T (65.52/43.87 kcal · mol^?1). But when adding one water molecule on the HNS, there is another special proton‐transfer isomerization pathway with a transition state 10T′ in which the water is out of the proton transfer loop. The corresponding forward/backward barriers are 65.89/65.89 kcal · mol^?1. Clearly, this process is more difficult to follow than the R–T–P process. For the two‐water‐assisting mechanism, the heat of reaction is 19.61 kcal · mol^?1, and the forward/backward barriers are 32.27/12.66 kcal · mol^?1, decreased by 33.25/31.21 kcal · mol^?1 compared with T. For trihydration and tetrahydration, the forward/backward barriers decrease as 32.00/12.60 (30T) and 37.38/17.26 (40T) kcal · mol^?1, and the heat of reaction decreases by 19.39 and 19.23 kcal · mol^?1, compared with T, respectively. But, when four water molecules are involved in the reactant loop, the corresponding energy aspects increase compared with those of the trihydration. The forward/backward barriers are increased by 5.38 and 4.66 kcal · mol^?1 than the trihydration situation. In the second mode, the outer‐sphere water effect from the other water molecules directly H‐bonded to the loop is considered. When one to three water molecules attach to the looped water in one‐water in‐loop‐assisting proton transfer isomerization, their effects on the three energies are small, and the deviations are not more than 3 kcal · mol^?1 compared with the original monohydration‐assisting case. When adding one or two water molecules on the dihydration‐assisting mechanism, and increasing one water molecule on the trihydration, the corresponding energies also are not obviously changed. The results indicate that the forward/backward barriers for the three in‐loop water‐assisting case are the lowest, and the surrounding water molecules (out‐of‐loop) yield only a small effect. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2006