镉(Ⅱ)-咪唑邻啡啰啉-氨基酸三元体系配位平衡

用 p H-电位滴定法测定了在 3 7°C,μ=0 .1 mol/L KNO3,3 0 %二氧六环 /水 (体积分数 )条件下 ,Cd(IP) (Aa) +三元配合物的平衡常数 lgβ及相对于二元配合物的表征常数Δlg K和 lg X。其中 IP为咪唑邻啡啉 ,Aa-分别为丙氨酸 (Ala-)、α-氨基己二酸 (Ami-)、精氨酸 (Arg-)、赖氨酸(Lys-)和酪氨酸 (Tyr-)。实验结果表明 ,Ami-、Arg-、Lys-和 Tyr-4个体系配合物Δlg K和 lg X均比相应的 Ala-体系大。从配体间的电子效应、疏水效应和氢键作用等方面对配合物的额外稳定性进行了讨论。     

镉(Ⅱ)-咪唑邻啡FDB3啉-氨基酸三元体系配位平衡

用pH-电位滴定法测定了在37°C,μ=0.1 mol/L KNO3, 30%二氧六环/水(体积分数)条件下,Cd(IP)(Aa)+三元配合物的平衡常数lgβ及相对于二元配合物的表征常数ΔlgK和lgX.其中IP为咪唑邻啡FDEC啉,Aa-分别为丙氨酸(Ala-)、α-氨基己二酸(Ami-)、精氨酸(Arg-)、赖氨酸(Lys-)和酪氨酸(Tyr-).实验结果表明,Ami-、Arg-、Lys-和Tyr- 4个体系配合物ΔlgK和lgX均比相应的Ala-体系大.从配体间的电子效应、疏水效应和氢键作用等方面对配合物的额外稳定性进行了讨论.     

镉（Ⅱ）—咪唑邻啡Luo啉—氨基酸三元体系配位平衡

用pH－电位滴定法测定了在37℃,μ＝0.1mol/L KNO3,30%二氧六环／水（体积分数）条件下,Cd（IP)(Aa)^ 三元配合物的平衡常数lgβ及相对于二元配合物的表征常数△lgK和lgX。其中IP为咪唑邻啡Luo啉,Aa^-分别为丙氨酸（Ala^-）、α－氮基已二酸（Ami^-）、精氨酸（Arg^-）、赖氨酸（Lys^-）和酪氨酸（Tyr^-）。实验结果表明,Ami^－、Arg^-、Lys^-和Tyr^-4个体系配合物△lgK和lgX均比相应的Ala^-体系大。从配体间的电子效应、疏水效应和氢键作用等方面对配合物的额外稳定性进行了讨论。     

锰(Ⅱ)咪唑二羧酸基超分子的水热合成、晶体结构和热性能

使MnCl2与2-(-萘基)-咪唑-4,5-二羧酸(H3NIDC)在甲醇和水的混合溶剂中水热反应,合成了一个新颖的超分子配合物[Mn(H2NIDC)2(H2O)2]。结构测试表明:在此配合物中,Mn(Ⅱ)与两个有机羧酸配体以及两个水分子六配位,处于八面体构型中。在其固态结构中,基本的单核单元在分子间作用力下形成了三维超分子。进一步研究了标题配合物的热稳定性能。     

二氰基二硫纶·邻菲咯啉-5,6-二酮混配锰(Ⅱ)、铁(Ⅱ)、钴(Ⅱ)配合物的感光氧化特性

测定了二氰基二硫纶·邻菲咯啉-5,6-二酮混配锰(Ⅱ)、铁(Ⅱ)、钴(Ⅱ)配合物MLL'(M=Mn2+、Fe2+、Co2+;L=mnt2-,1,2-二氰基乙烯-1,2-二硫醇离子;L'=phen-5,6-dione,1,10-邻菲咯啉-5,6-二酮)在二甲基亚砜(DMSO)、丙酮(Acet)和氯仿(CHCl3)中的电子...     

硫酸铵-碘化钾-十二烷基二甲基苄基溴化铵体系浮选分离镉(Ⅱ)

建立了硫酸铵-碘化钾-十二烷基二甲基苄基溴化铵体系浮选分离镉(Ⅱ)的新方法,探讨了镉(Ⅱ)与常见离子定量分离的条件。结果表明,控制pH=4.0,利用硫酸铵-碘化钾-十二烷基二甲基苄基溴化铵体系可使Cd~(2+)被定量浮选,而Zn~(2+)、Co~(2+)、Mn~(2+)、Ni~+、A1~(3+)等不被浮选,实现了Cd~(2+)与这些离子的定量分离。方法用于环境水样中微量Cd~(2+)的定量浮选分离,回收率为95.6%~102.3%。     

硫酸铵-碘化钾-十二烷基三甲基溴化铵-水体系浮选分离镉(Ⅱ)的研究

研究了硫酸铵一碘化钾-十二烷基三甲基溴化铵-水体系浮选分离镉(Ⅱ)的行为及其与常见离子分离的条件.结果表明,当固体(NH4)2SO4用量为1.0g,0.10mol/L碘化钾溶液和5.0×10-3mol/L十二烷基三甲基溴化铵(DTAB)溶液的用量均为1.0mL时,体系中形成的不溶于水的三元缔合物(DTAB)2(Cdl4)可浮于盐水相上形成界面清晰的两相,从而Cd2 被定量浮选,而Zn2 、Mn2 、Ni2 、Co2 、Fe2 、Al3 等在此条件下不被浮选,实现了Cd3 与这些离子的定量分离,据此建立了浮选分离镉(Ⅱ)的方法.该方法对合成水样中微量镉进行了定量浮选分离,浮选率为97.1%～103.0%.     

氧化石墨烯-吖啶橙荧光光度法测定镉(Ⅱ)离子

在碱性介质中,氧化石墨烯吸附吖啶橙(AO),对AO的荧光可产生猝灭作用,加入适量镉(Ⅱ)离子,体系在526 nm处的荧光增强,ΔF值与镉(Ⅱ)离子浓度在2.97×10^(-8)(-8)⁴.40×104.40×10^(-7)mol/L范围内呈良好线性关系,线性回归方程为ΔF=5.318 c(10(-7)mol/L范围内呈良好线性关系,线性回归方程为ΔF=5.318 c(10^(-8)mol/L)+13.34,r=0.997 0,检测限为8.90×10(-8)mol/L)+13.34,r=0.997 0,检测限为8.90×10^(-9)mol/L,相对标准偏差为1.58%(-9)mol/L,相对标准偏差为1.58%².52%。本方法操作简便、快速、仪器设备简单,已用于实际样品测定,结果满意。     

氧化石墨烯-吖啶橙荧光光度法测定镉(Ⅱ)离子

在碱性介质中,氧化石墨烯吸附吖啶橙(AO),对AO的荧光可产生猝灭作用,加入适量镉(Ⅱ)离子,体系在526 nm处的荧光增强,ΔF值与镉(Ⅱ)离子浓度在2.97×10~(-8)~4.40×10~(-7)mol/L范围内呈良好线性关系,线性回归方程为ΔF=5.318 c(10~(-8)mol/L)+13.34,r=0.997 0,检测限为8.90×10~(-9)mol/L,相对标准偏差为1.58%~2.52%。本方法操作简便、快速、仪器设备简单,已用于实际样品测定,结果满意。     

2-巯基吡啶镉(Ⅱ)、汞(Ⅱ)配合物的热分解动力学研究

采用TG-DTG技术研究了2-巯基吡啶镉(Ⅱ)、汞(Ⅱ)配合物在氮气气氛中的热分解机理及非等温动力学。采用积分法(Coats-Refern方程,HM方程,MKN方程)和微分法(Achar方程)对非等温动力学数据进行了分析,得到了配合物第一步热分解反应的机理函数、动力学参数和热分解动力学方程。结果表明:其热分解过程属F2(化学反应)机理控制,非等温热分解的动力学方程为dα/dT=A/β.e-E/RT(1-α)2,其中镉(Ⅱ)配合物的表观活化能E=86.35 kJ/mol,指前因子A=4.72×107s-1;汞(Ⅱ)配合物的表观活化能E=189.67 kJ/mol,指前因子A=3.79×1018s-1。     

Synthesis and Characterization of Pure Phase Zn(II) and Cd(II) Oxide Nanoparticles via Thermal Decomposition of Four New Zn(II) and Cd(II) Coordination Polymers

Four new Zn(II) and Cd(II) coordination polymers, [Zn(2-AMP)₂(N₃)₂]_n (1), [Zn(2-AMP)₂(SCN)₂]_n (2), [Cd(2-AMP)(N₃)₂]_n (3) and [Cd(2-AMP)₂(SCN)₂]_n (4) {2-AMP: 2-Aminomethylpyridine}, have been synthesized and characterized by single crystal X-ray diffraction, IR spectroscopy and elemental analyses. The Zinc(II) oxide and Cadmium(II) oxide nano-particles have been synthesized from thermolysis of 1–4 at 600 °C under air atmosphere for 4 h. The ZnO and CdO nanoparticles were characterized by X-ray diffraction and scanning electron microscopy (SEM). SEM images show the average size of produced ZnO and CdO nanoparticles are 60–70 nm in all compounds.     

A Novel Twofold Interpenetrating 2D (3,5)-Connected Cd(II) Coordination Framework with (52.6)(55.64.7) Topology

The self-assembly of 4′-(4-carboxyphenyl)-4,2′:6′4″-terpyridine (HL) with Cd(II) cation afforded one novel twofold interpenetrating 2D coordination polymer, [Cd(L)₂(H₂O)_1.5] _n . In this compound, the Cd(II) atoms as 5-connected nodes are linked by the bridging ligands L acting as both linear connectors and 3-connected nodes to form a novel (3, 5)-connected 2D framework with the (5².6)(5⁵.6⁴.7) topology. Two equivalents of such 2D framework interpenetrate with each other to form a more complicated supramolecular network. Furthermore, fluorescent measurement on the powder sample shows that the complex strongly emits at 399 nm with the excitation of 331 nm.     

Hydrothermal Synthesis, Characterization of Mn(II) and Cd(II) Coordination Polymers Assembled from Semi-Rigid Oxo-Bridged Carboxylate and N-Donor Ligands

Two new metal–organic coordination polymers containing Mn(II) and Cd(II) with oxo-bridged and N-donor ligands, [Mn(oba)(2,2′-bipy)] _n (1) and {[Cd(oba)(bib)]·H₂O} _n (2) [2,3′-H₂oba = 2-(3-carboxyphenoxy)benzoic acid, 2,2′-bipy = 2,2′-bipyridine, and bib = 4,4′-bis(2-methylimidazole-1-ylmethyl)biphenyl], have been prepared and characterized by elemental analysis, Fourier infrared spectroscopy, and X-ray diffraction. Complex 1 has a 3D supramolecular network constructed from 1D zigzag chain via π–π stacking interactions. Complex 2 features 1D ladder-like chain which consists of 1D helical arrays and bib pillars. Moreover, photoluminescence properties of the bib ligand and the Cd(II) complex were investigated.     

Four Flexible Bis(Thiabendazole)-Based Cd(II) Coordination Polymers with Various Aromatic Carboxylates: Syntheses,Structures and Properties

Four Cd(II) coordination polymers (CPs) including [Cd(btbb)_0.5(L1)] _n (1), [Cd(btbb)(L2)·(H₂O)_1.5] _n (2), [Cd(btbb)(L3)] _n (3), and [Cd(btbb)(HL4)] _n (4) (btbb?=?1,4-bis(thiabendazole)butane, H₂L1?=?5-hydroxyisophthalic acid, H₂L2?=?4,4′-biphenyldicarboxylic acid, H₂L3?=?tetrabromoterephthalic acid, H₃L4?=?5-nitro-1,2,3-benzenetricarboxylic acid) were prepared under hydrothermal conditions based on flexible bis(thiabendazole) ligand and different co-carboxylates. Their structures have been determined by single-crystal X-ray diffraction analyses, elemental analyses, IR spectra, X-ray powder diffraction, and thermogravimetric analyses. CP 1 exhibits a 3D 2-nodal (3,4)-connected framework with the 3,4T10 topology. CP 2 and 3 feature typical hcb layer structure, and 3 is further combined into a 3D supramolecular architecture through C–H?O hydrogen bonds. CP 4 possesses an infinite chain and further extended into 2D supramolecular network by O–H?O hydrogen-bonding interactions. The effects of the aromatic polycarboxylate co-ligands on the CPs framework have been discussed and the catalytic activities of CPs 1–4 for degradation of methyl orange in Fenton-like process are also investigated.     

Ancillary Ligand-Mediated Syntheses,Structures and Fluorescence of Three Zn/Cd(II) Coordination Polymers Based on Nitrobenzene Dicarboxylate

The Zn/Cd(II)-nbdc carboxylate motifs mediated by various dipyridyl-typed ligands afforded three new coordination compounds, namely, [Zn(nbdc)(bpa)_0.5(H₂O)]·H₂O (1), [Zn₂(nbdc)₂(bpp)₂]·H₂O (2), and [Cd(nbdc)(bpe)_0.5(H₂O)₂] (3) (H₂nbdc = 4-nitrobenzene-1,2-dicarboxylic acid, bpa = 1,2-bi(4-pyridyl)ethane, bpe = 1,2-di(4-pyridyl)ethylene, and bpp = 1,3-bis(4-pyridyl)propane), which were synthesized by hydrothermal reaction and characterized by elemental analysis, IR, thermal analysis (TGA), and fluorescent analysis. The single-crystal X-ray diffractions reveal that three complexes display a diverse range of connectivity topology from 1D to 3D, which is dependent on the type of dipyridyl-typed ligands and metal centers. Complex 1 is the 1D chain featuring Zn-carboxylate binuclears extended further by bpa coligands. Complex 2 is the 2D thick-layer containing double-stranded chains cross-linked further by bpp coligands. Complex 3 is the 3D framework with (6³)(6⁵.8) ins topology featuring Cd-carboxylate chiral layers pillared by bpe coligands. The thermal stabilities and fluorescence properties for complexes 1–3 are investigated.     

Imidazole-Containing Ligands Assisted Self Assembly of Two New Cd(II) Coordination Polymers: Syntheses, Crystal Structures and Photoluminescent Properties

Two new coordination polymers, {[Cd₂(PDC)₂(H₂O)₂(L₁)]·2H₂O}_n (1) and {[Cd (2,5-PDC)(H₂O)(L₂)]·H₂O}_n (2), have been obtained from hydrothermal reactions of Cd²⁺ ion with the 2,5-pyridinedicarboxylic acid (H₂PDC) and two imidazole-containing ligands [L₁ = 1,4-bis(imidazol-1-yl)benzene and L₂ = 1,4-bis(1-imidazol-yl)-2,5-dimethylbenzene]. Complex 1 features a three-dimensional 6-connected rob topological net. Complex 2 shows a two-dimensional 6-connected hxl topological net. The structural differences between 1 and 2 demonstrate that the different imidazole-containing ligands play critical roles in the formation of the resulting frameworks. The photoluminescent properties of 1 and 2 have also been investigated.