饱和锌的粘土矿物吸附半胱氨酸的机理

用红外光谱、X射线衍射（XRD）和热分析研究了饱和过渡金属锌的粘土矿物吸附半胱氨酸的机理；XRD结果显示吸附了半胱氨酸后的粘土矿物的d(001)方向的距离明显增大，说明被吸附的半胱氨酸进入了粘土的层状结构之中；饱和了锌的粘土矿物吸附半胱氨酸有两种方式，其一为弱相互作用，另一种强相互作用；后一种方式吸附的半胱氨酸与粘土的过渡金属之间形成了配合结构，结合力比较强，在热作用下，它们一直到395℃左右才分解；强相互作用吸附的半胱氨酸主要是以去质子的两性离子和阴离子形式存在于粘土矿物上，与过渡金属形成螯合的六元环结构。     

Influences of permeation of vanadium ions through PVDF-g-PSSA membranes on performances of vanadium redox flow batteries

The preparation and physical characterization of a poly(vinylidene fluoride)-graft-poly(styrene sulfonic acid) (PVDF-g-PSSA) membrane prepared by a solution-grafting method were described. These membranes exhibited high conductivity with a value 3.22 x 10(-2) S/cm at 30 degrees C. ICP studies revealed that the PVDF-g-PSSA membrane showed dramatically lower vanadium ion permeability compared to Nafion 117. Trivalent vanadium ions had the highest permeability through all these membranes in contrast to pentavalent vanadium ions with the lowest. The VRB with the low-cost PVDF-g-PSSA membrane exhibited a higher performance than that with Nafion 117 under the same operating conditions, and its energy efficiency reached 75.8% at 30 mA/cm(2). The performance of VRB with the PVDF-g-PSSA membrane can be maintained after more than 200 cycles at a current density of 60 mA/cm(2).     

(C2H10N2)[BPO4F2] — Structural Relations between [BPO4F2]2— and [Si2O6]4—

(C₂H₁₀N₂)[BPO₄F₂] — Strukturbeziehungen zwischen [BPO₄F₂]^2— und [Si₂O₆]^4— Colourless crystals of (C₂H₁₀N₂)[BPO₄F₂] were prepared from mixture of ethylendiamine, H₃BO₃, BF₃ · C₂H₅NH₂, H₃PO₄ and HCl under mild hydrothermal conditions (220 °C). The crystal structure was determined by single crystal methods (triclinic, P1¯ (no. 2), a = 451.85(5) pm, b = 710.20(8) pm, c = 1210.2(2) pm, α = 86.08(1)°, β = 88.52(2)°, γ = 71.74(1)°, Z = 2) and contains infinite tetrahedral zweier‐single‐chains {[BPO₄F₂]^2—} which are isoelectronic (48e^—) with the polyanions {[Si₂O₆]^4—} of the pyroxene family.     

Effects of Self—coiling of Organic Molecules on Intramolecular Exciplex Formation and Fluoresscence Quenching in DX—H2O Solvent System

Effects of self-coiling of organic molecules on intramolecular exciplex formation of compound I,in which the carbazole chromophore and terephthalic acid methylester acceptor group are linked by one (CH2)10 chain,and the decrease of the fluorescence intensities of compounds Ⅱ，Ⅲ，and Ⅳ,in which the carbazole chromophore and 3,5-dinitrobenzoate are connected by one aliphatic chain of (CH2)10 (Ⅱ），（CH2）12（Ⅲ）,or (CH2)4(Ⅳ）,have been studied in the dioxane (DX)-H2O binary system.The results show that self-coiling of organic molecules in DX-H2O facilitates intramolecular exciplex formation of I and induces the decrease of fluorescence intensities of Ⅱ,bacause of the proximity effect brought about by selfcoiling of organic molecules under hydrophobic-lipophilic interaction(HLI) between the excited carbazole chromophore and the acceptor.Since the similar effects are observed even when the concentration of the probes are less than their CAgCs(critical aggregate concentrations )in the DX-H2O mixture with the same φ values,formation of the intermolecular exciplex has been excluded.The effects are found to be strongly depended on φ values,indication that they are mainly driven by HLI.The properties of the acceptors can also affect the intramolecular exciplex formation.With terephthalic acid methylester moiety as the acceptor,the carbazole chromophore exhibits the fluorescence spectra of the exciplex,while with 3,5-dinitrobenzoate moiety as the acceptor,only the fluorescence spectra of excited carbazolyl chromophore are observed.     

光谱电化学法研究亚甲基蓝的电还原反应

用极谱法研究亚甲基蓝(MB)的电极吸附过程早有报道.近几年,用光谱电化学法研究其电化学行为又引起了许多人的兴趣.但在光透薄层电极上,由于光程太短,测试溶液浓度较高,导致亚甲基蓝发生聚合,影响实验结果的准确测定.为此本文利用特制的比色皿型长光程薄层光谱电化学池,在低浓度条件下研究其在SnO_2镀膜玻璃电极上的电还原反应.     

Patterned polyelectrolyte multilayer: surface modification for enhancing selective adsorption

This paper describes the use of surface chemical modification to enhance the difference of the surface charge on a patterned polyelectrolyte multilayer, which can be used for selectively adsorbing functional materials. We fabricated a patterned multilayer by combining the layer-by-layer self-assembly technique and photolithography and taking advantage of the different solubility of polyelectrolyte multilayers of diazo resins (DAR)/poly(acrylic acid) before and after UV irradiation. This patterned surface can be used as a matrix for selective adsorption of small molecular dyes, such as Methylene Blue. However the difference in surface charge on the patterned surface was not enough when we used it to selectively adsorb polystyrene (PS) nanoparticles using electrostatic force as the driving force. Therefore, we modified the patterned surface by interfacial chemistry. After modification, the patterned polyelectrolyte multilayer can be used as a good matrix for selective adsorption of PS nanoparticles with both positive and negative charges.     

分子电子学的新进展

分子尺度电子学通过构筑基于微尺度电极和单个分子或者少量分子聚集体的"电极-分子-电极"结，研究跨越分子的电荷输运性质.它将分子本征化学特性与器件构筑相结合，考察分子的理化特性与电荷输运的构效关系，揭示微尺度的量子输运动力学原理，并探索基于分子的功能电子器件.是一个集化学、物理学与微电子学为一体的交叉学科.总结整理了分子电子学近些年在器件制备、输运机理及应用方面部分有代表性的进展.     

Preparation and Characterization of Three-dimensionally Ordered Crystalline Macroporous CeO2

Three-dimensional ordered macroporous (3DOM) materials are of great potential importance in catalysis, selective separation, sensor arrays and communications with optical band gaps1. Many results in the synthesis of 3DOM materials have been reported, such as closed-packed silica spheres or polystyrenes (PS) templating routes for silica2, metal oxides1-6 and metals7. Recently, poly(methyl methacrylate) (PMMA) colloidal crystal templates have been used to prepare 3DOM materials of metals8,…     

连接基团链长度对季铵盐二聚表面活性剂C12-s-C12·2Br在水溶液中胶团化行为的影响

用电导法、稳态荧光法和粘度法研究了二聚表面活性剂C12-s-C12*2Br分子中的连接基团链长度(s=2, 3, 4, 6)对其在水溶液中聚集行为的影响. 实验发现, C12-s-C12*2Br的胶团生成能力远比其单体C12TABr强得多, 前者cmc值较后者降低一个数量级. 胶团聚集数N随表面活性剂浓度c的增大而增大, 其中当s=2时的N值在c=7.7 mmol/L后开始急剧增大. 计算结果表明, 此时胶团形状发生了明显变化, 形成了椭球形的胶团. 粘度测定结果也证实了这一点.     

Investigation on solvent casting films of surfactant-encapsulated clusters

The surfactant-encapsulated cluster (SEC) composed of a hydrophobic dimethyl dioctadecyl ammonium (DODA) shell and an encapsulated hydrophilic polyoxoanion core can form casting films. The structure of the casting film is influenced by evaporation rates of organic solvent. When the casting films are prepared by slow evaporation of chloroform, the alkyl chains are considered to possess a partial interdigitation, and the interdigitated length is 1.6 nm. The casting film structure is characterized by scanning force microscopy (SFM), Fourier transformation infrared (FT-IR), wide-angle X-ray diffraction, and differential scanning calorimetry (DSC).