具有三维阵列结构的树枝晶CdS的制备及生长机理研究

采用电沉积和溶剂热相结合的方法,以树枝状金属Cd颗粒为模板和前驱体,在乙二胺溶剂中以六亚甲基四胺(HMTA)为表面修饰剂,制备出具有三维阵列结构的树枝晶CdS。利用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)结合X射线能谱仪(EDS)等对样品的物相、形貌、元素组分和结构进行了分析。结果表明:在溶剂热反应过程中,当不加入HMTA时,得到的产物是无序的CdS纳米线;而在HMTA的作用下,则生成的是具有三维阵列结构的树枝晶CdS;通过分析溶剂热反应过程中的化学反应,并结合产物形貌演变规律,提出了具有三维阵列结构的树枝晶CdS的形成机理。光催化性能测试表明具有三维树枝晶CdS纳米阵列在可见光照射下表现出良好的光催化活性。     

Preconcentration of chlorophenols in water samples using threedimensional graphene-based magnetic nanocomposite as absorbent

In this paper, a novel magnetic solid-phase extraction method using three-dimensional graphene-based magnetic nanocomposite as adsorbent for the preconcentration of several chlorophenols from water samples prior to high-performance liquid chromatography analysis was developed. Various experimental parameters were investigated. Under the optimum conditions, the enrichment factors of the method were in the range of 186–312, and the limit of detection(S/N = 3) was 0.10 ng/mL. The recoveries of the method were in the range between 85.1% and 101.2%. The developed method has been successfully applied to the determination of chlorophenols in environmental water samples.     

三维荧光结合二阶校正法测定绞股蓝中槲皮素含量

采用三维荧光并结合二阶校正的平行因子分析(PARAFAC)算法、交替三线性(ATLD)算法和自加权交替三线性(SWATLD)算法对中药绞股蓝中的槲皮素含量和回收率进行测定,Al(Ⅲ)作敏化剂增加槲皮素的荧光强度。核一致检验法说明体系中荧光组分数为2,其中一个组分对应于槲皮素,另一个对应于中药中的一个共存组分。3种方法测定中药绞股蓝中槲皮素的含量分别为0.274 9%,0.272 9%和0.272 7%,回收率分别为96.3%,103.1%和96.8%,得到的槲皮素解析光谱和真实光谱几乎完全重合。实验结果表明,化学计量学"二阶校正"法具有简单、快速、高效及操作费用低等特点,可用于复杂成分的定性和定量分析。同时,还讨论了中药溶液中内滤光效应对荧光强度及定量分析的影响,并采用数学校正法对中药溶液的内滤光效应进行校正,实验发现测定的荧光强度用相应的溶液吸光度校正后,定量分析结果的准确度大大改善。     

A Novel 3D Heterobimetallic Cyano-bridged Coor- dination Polymer {（NH4）2[Cd（H20）Fe（CN）6]}n： Synthesis and Crystal Structure①

A novel heterobimetaUic coordination polymer, {（NH4）2[Cd（H20）Fe（CN）6]}n 1, has been synthesized by using the slow diffusion method and structurally characterized by elemental analysis, 1R spectroscopy and single-crystal X-ray diffraction. The crystal crystallizes in the monoclinic system, space group P21/n, a = 7.4202（16）, b = 14.939（3）, c = 10.868（2） A and ,8 = 91.660（3）°. For 1, five CN groups of Fe（CN）6]4- are involved in bridging. The polymer displays a 3D open microporous framework with 5-connected uninodal （46.64） topology.     

Synthesis and Characterization of Two Binuclear Macrocyclic Zinc(Ⅱ) Complexes by Anion Exchange

Two macrocyclic zinc(II) complexes {[ZnL(VO3)2]·0.33H2O}n(1) and [ZnL(H2O)2][Ni(CN)4](2)(L = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) have been obtained from the reactions of [ZnL](ClO4)2 with NH4VO3 and K2[Ni(CN)4], respectively, and structurally characterized by elemental analysis, IR, XRPD, TG and X-ray diffraction. Single-crystal X-ray diffraction analyses indicated that the Zn(II) atom lies on an inversion center and is octahedrally coordinated by four nitrogen atoms of the tetradentate macrocyclic ligand in the equatorial plane and two oxygen atoms of [VO4] tetrahedra in the axial positions in 1, and two oxygen atoms of two water molecules in 2. Complex 1 shows a three-dimensional structure, which is constructed by the links of [VO3]nn- chains with [ZnL]2+, forming one-dimensional channels occupied by guest water molecules. The monomers of [ZnL(H2O)2]2+ and [Ni(CN)4]2- are connected through the intermolecular hydrogen bonds to form a two-dimensional sheet in complex 2.     

Synthesis,Crystal Structure and Photoluminescence of a Three-coordinate Ag(Ⅰ) Complex

A three-coordinate Ag(I) complex, [Ag(Mepzpy)(PAr3)]BF4·H2O(1, Mepzpy = 3-methyl-1-(2-pyridyl)pyrazole, PAr3 = tri(o-tolyl)phosphine), was synthesized from the reaction of Ag(CH3CN)4BF4, PAr3 and Mepzpy in CH3 CN at room temperature. The compound was characterized by UV-vis, NMR and X-ray single-crystal structure analysis. It crystallizes in triclinic space group P1 with a = 10.2251(5), b = 10.6014(5), c = 15.7012(5) , α = 92.963(3), β = 92.641(3), γ = 114.647(4)o, V = 1540.6(1) 3, Z = 2, Mr = 676.24, Dc = 1.458 g/cm3, F(000) = 688, μ = 6.187 mm-1, GOOF = 1.038, the final R = 0.0530 and w R = 0.1493 for 6371 observed reflections with I 2σ(I). Compound 1 is ionic. It is composed of a BF4- anion and a [Ag(Mepzpy)(PAr3)]+ cation. The Ag(I) ion adopts a distorted trigonal pyramidal coordination geometry defined by two nitrogen atoms and a phosphorous atom. The complex emits blue luminescence with maximum peaks at 470 nm in solid state at room temperature.     

磺酰脲类乙酰羟基酸合成酶抑制剂的拓扑物比较分子力场分析

磺酰脲类除草剂是一类高选择性、广谱、低毒的化合物,在世界范围内得到了广泛的应用。本文采用拓扑物比较分子力场分析(Topomer-CoMFA)对75个磺酰脲类化合物与植物源野生型拟南芥AHAS酶的离体相互作用进行了三维定量构效关系研究,构建了Topomer CoMFA模型,该模型具有较强的预测能力(交叉验证相关系数q2为0.890,非交叉验证相关系数r2为0.967)。此模型对测试集的10个化合物的pKi值进行预测,其预测值与实际值基本一致。     

基于吡咯并吡咯二酮核心的苝二酰亚胺类受体分子的合成及光伏性能

苝二酰亚胺类小分子由于其固有的强分子聚集特性,导致活性层形貌难于调控,器件效率相对于近年来报道的受体-给体-受体型稠环小分子受体一直处于劣势.针对这一关键问题,我们设计并合成了三个以吡咯并吡咯二酮为中心核的双臂型和四臂型苝二酰亚胺类小分子受体.其中,c-PDI2和nc-PDI2两个双臂型分子分别将两个苝二酰亚胺臂置于吡咯并吡咯二酮核心骨架的碳取代位和氮取代位;四臂型PDI4是将四个苝二酰亚胺臂置于吡咯并吡咯二酮核心骨架的四个取代位.通过对三个受体小分子的光谱吸收、能级水平、薄膜形貌以及光伏性能的详细研究,发现三个受体小分子都拥有扭曲的分子结构并由此带来无定形薄膜形貌,表明其分子聚集趋势得到了有效的抑制.相对于双臂型受体分子,四臂型PDI4具有更强的光吸收能力和电子传输性能,从而获得了8.45%的最高光电转换效率,是c-PDI2器件效率的2倍和nc-PDI2器件效率的1.5倍.     

复杂应力状态下GCr15轴承钢的动态剪切及熔融特性研究

本文探究了GCr15轴承钢压剪试样在冲击载荷下的绝热剪切和熔融破坏特性．首先,实验研究发现GCr15轴承钢的力学性能具有拉-压不对称性、应力状态及应变率敏感性．因此,通过引入应力三轴度、洛德角、应变率和绝热剪切温升机制扩展了经典J-C本构模型,并对GCr15轴承钢的动态单轴压缩和压剪试验结果进行了数值实现．研究结果表明,应力三轴度和洛德角是影响动态冲击下压剪试样的绝热剪切产生和熔融特性的重要因素．     

三维立方准晶椭球夹杂的Eshelby张量

准晶体颗粒复合智能材料具有优异的物化性能和应用前景。不同于传统的各向同性材料,三维立方准晶体材料包含声子场,相位子场,及声子-相位子耦合场。为更好地研究准晶体颗粒夹杂问题,揭示准晶体材料夹杂问题的物理现象,本文利用本征应变公式和柯西留数定理,考虑椭球体夹杂,获得了三维立方准晶材料夹杂问题的Eshelby张量,并给出了统一的表达式。进而,当三维立方准晶夹杂形状为球形、棒状、扁平状和带状时,获得了封闭形式的三维立方准晶Eshelby张量表达式。同时,给出了椭球体长径比变化时Eshelby张量的变化规律,这对研究准晶体颗粒夹杂问题具有重要的理论意义。