Syntheses,Structures,and Properties of Two New Coordination Polymers Based on Tetracarboxylate and 2,2′-Bipyridine Mixed Ligands

Two new coordination polymers {[Zn2L1(2,2'-bpy)2(H2O)2]·4H2O}n(1) and [Zn2L2(2,2'-bpy)2(H2O)2]n(2)(H4L1 = terphenyl-2,2',4,4'-tetracarboxylic acid, H4L2 = quarterphenyl-2,2',4,4'-tetracarboxylic acid, and 2,2'-bpy = 2,2'-bipyridine) have been synthesized and characterized by elemental analysis, IR and X-ray single-crystal diffraction studies. Complex 1 displays 2D wavelike networks, which are further joined together through O–H···O hydrogen bonds to give a 3D supramolecular network. Complex 2 exhibits 1D ladder-like chains, and they are further joined together by π-π stacking and O–H···O hydrogen bonding interactions to form a 3D supramolecular network. The results indicate that the backbone of carboxylate ligands has significant effects on the formation and structure of the resulting functional coordination polymers. Additionally, thermal stability and photoluminescent properties of 1 and 2 are also investigated in detail.     

碳酸二甲酯在锌铝复合氧化物上分解行为的红外研究

采用尿素热分解法制备锌铝水滑石,1 073 K下煅烧得到相应的锌铝复合氧化物催化剂。通过XRD谱图确定锌铝复合氧化物ZAO-3(1 073 K)催化剂的组分为ZnO相和ZnAl2O4尖晶石相。NH3(CO2)-TPD结果表明,当向ZnO中引入Al后,催化剂的酸碱性位和酸碱性强度都发生改变。采用原位红外(in-situ FT-IR)手段,研究了碳酸二甲酯(DMC)分别在ZAO-3(1 073 K)、ZnAl2O4、ZnO上随着温度变化的分解行为。结果表明,ZAO-3(1 073 K)催化剂上大量的弱酸碱性位协同稳定DMC,抑制DMC的分解。     

以类水滑石为前驱体的Cu/Zn/Al/(Zr)/(Y)催化剂制备及其催化CO_2加氢合成甲醇的性能

采用共沉淀法合成了Cu:Zn:Al:Zr:Y原子比分别为2:1:1:0:0、2:1:0.8:0.2:0、2:1:0.8:0:0.2和2:1:0.8:0.1:0.1的Cu/Zn/Al/(Zr)/(Y)类水滑石化合物.将前驱体材料在空气中500°C焙烧后得到复合金属氧化物,并将其用于CO2加氢合成甲醇反应.采用X射线衍射(XRD)、热重(TG)分析、N2吸附、氧化亚氮(N2O)反应吸附、氢气程序升温还原(H2-TPR)和H2/CO2程序升温脱附(H2/CO2-TPD)技术对所制备的样品进行表征.结果表明,Zr和Y的引入使得催化剂BET比表面积大幅增加,金属铜的比表面积和分散度均按以下顺序依次增加:Cu/Zn/AlCu/Zn/Al/ZrCu/Zn/Al/YCu/Zn/Al/Zr/Y,然而,强碱位数目占总碱位数目的比例的变化顺序为:Cu/Zn/AlCu/Zn/Al/YCu/Zn/Al/Zr/YCu/Zn/Al/Zr.活性评价结果揭示CO2转化率取决于金属铜的比表面积,甲醇选择性则随强碱位比例的增加而线性增加.因而,Zr和Y的引入有利于甲醇的合成,Cu/Zn/Al/Zr/Y催化剂上的甲醇收率最高.     

Two 3-D Neutral Zn(Ⅱ)-MOFs Generated from the Asymmetric Schiff-base Ligand

Two new Zn(Ⅱ)-MOFs were synthesized based on an asymmetric Schiff-base ligand LH, which is obtained by the condensation of 5-formyl-8-hydroxyquinoline and 3-pyridinecarboxylic acid hydrazide. In different mixed solvents, we get two new isomorphism compounds, [Zn(L)2]·C4H8O2·2MeOH(1) and [Zn(L)2]·CH2Cl2·2MeOH(2). Compounds 1 and 2 have been characterized by single-crystal X-ray diffraction, elemental analysis and IR. Compound 1 crystallizes in monoclinic, space group P21/c, with a = 13.856(4), b = 14.156(4), c = 9.620(3) , β = 110.167(5)°, V = 1771.3(9) 3, Dc = 1.500 g/cm3, C38H38N8O8 Zn, Mr = 800.13, F(000) = 832, μ(MoKα) = 0.761 mm-1, Z = 2, the final R = 0.0596 and wR = 0.1221 for 2112 observed reflections(I 2σ(I)). Compound 2 belongs to monoclinic, space group P21/c, with a = 13.575(3), b = 14.130(3), c = 9.485(2) , β = 107.908(3)°, V = 1731.2(6) 3, Dc = 1.529 g/cm3, C35H32Cl2N8O6 Zn, Mr = 796.96, F(000) = 820, μ(MoKα) = 0.926 mm-1, Z = 2, the final R = 0.0527 and wR = 0.1395 for 2501 observed reflections(I 2σ(I)). The Zn(Ⅱ) centers in both 1 and 2 display a distorted octahedral coordination geometry. The octahedral Zn(Ⅱ) nodes and L linkages build up 2-D nets consisting of parallelogram-like grids in the ab plane. The neighboring nets stack through hydrogen bonds to generate 3-D rhombic channels. In 1, the 1,4-dioxane and MeOH guests alternatively arrange in the channels and effectively take up the free space; while in 2, the CH2Cl2 guests are arranged in the channels. In addition, the encapsulated MeOH molecules are bonded to the framework by hydrogen bonds.     

Preparation and characterization of aqueous polyaniline battery using a modified polyaniline electrode

A rechargeable battery of the type Zn/ZnCl₂, NH₄Cl/polyaniline (PAn)-reticulated vitreous carbon was successfully prepared based on a PAn modified electrode. Voltage of the battery was 1.2 V. Charge-discharge behavior at a constant load of 2.5 k, recycle ability and the rate of self-discharge were measured. The results showed that the battery has a capacity of 121 mA h g⁻¹ polymer weight and coulombic efficiency was in the range between 75% and 100%. Self-discharge rate was less than 1% per day and the battery showed a good recycle ability. It was also found that even after 70 cycles, the decrease in the open-circuit voltage was less than 5%.     

罗丹明B合锌（Ⅱ）配合物的合成,分子结构与性质研究

合成了ＲＢ－Ｚｎ配合物,晶体结构分析结果表明配合物组成为「Ｚｎ（ＲＢ）（ＯＡｃ）２（Ｈ２Ｏ）」晶体属单斜晶系、空间群为Ｐ２１／ｎ（＃１４）,晶胞参数为ａ＝１．０２９８（２）ｎｍ,ｂ＝１．８９０１（４）ｎｍ,ｃ＝１．６６６０（６）ｎｍ;β＝１０５．２４（３）°;Ｚ＝４,Ｄｃａｌ＝１．３６７ｇ／ｃｍ＾３。研究了配合物的物质的量电导,ＩＲ和荧光光谱,同时对配体配合物的半导体行为进行了考察。     

血清锌、铜与铜/锌比值对肺癌诊断、疗效和预后判断的临床意义

测定了天津市第一中心医院自１９９６年１月－１９９８年１２月收治的５６例肺癌患者和６０例健康者（对照组）血清锌、铜含量和铜／锌比值,发现肺癌锌明显于对照组,铜与血清铜／锌比值明显高于健康对照组。还发现肺癌组按ＴＮＭ分期,其铜与铜／锌比值各期均较对照组明显增高,且随病性进展而增高。     

完全脱乙酰化壳聚糖与Zn(Ⅱ)的配位作用

在均相反应条件下 ,完全脱乙酰化的壳聚糖与ZnSO4 进行配位反应 .用元素分析、IR、固体13 C NMR、UV vis、TGA和X 衍射等表征方法研究了Zn(Ⅱ )与壳聚糖所形成配位聚合物的组成和结构 .在pH =7时 ,一个Zn(Ⅱ )与二个壳聚糖重复单元中的氨基和仲羟基进行了配位     

ChemInform Abstract: SrZn2Sn2 and Ca2Zn3Sn6 — Two New Ae—Zn—Sn Polar Intermetallic Compounds (Ae: Alkaline Earth Metal).

The title compounds are synthesized from the elements (950—1000 °C, 45 min—48 h) and characterized by single crystal XRD and DFT electronic structure calculations.     

[Ru(bpy)_2tpphz]~(2+)与Zn~(2+)形成的双核配合物的荧光性质研究

近年来,钌多吡啶配合物与DNA的作用得到了比较广泛的研究,并且发展了一系列具有特定功能的钌配合物犤1犦。如传统的DNA分子光开关犤Ru(bpy)2dppz犦2+和犤Ru(phen)2dppz犦2+犤2,3犦(bpy=2,2'-联吡啶,phen=1,10-菲咯啉,dppz=二吡啶犤3,2-a:2',3'-c犦吩嗪)。这些配合物与DNA具有较强的结合力,在水溶液中几乎不发光,但在DNA存在下则有强烈荧光发出。这是由于配合物插入DNA的碱基对之后,保护了dppz的吡嗪环上的N原子,使其免受水分子的进攻从而导致配合物荧光的恢复。但是对于大多数的多吡啶钌配合物来讲,由于其自身较强的背景荧光或与DN…