Preparation and characterization of novel organic chelating resin and its application in recovery of Zn(II) from aqueous solutions

An organic polymeric resin was synthesized by anchoring p ‐aminobenzoic acid onto macroporous chloromethylated polystyrene beads, and was used for Zn(II) removal from aqueous solutions. The resin exhibited an initially rapid adsorption property for Zn(II) with equilibrium time of 10 h and the maximum adsorption capability approached 184.5 mg g⁻¹. Optimum pH was 4.5. The mechanism of adsorption was investigated using kinetic, isotherm and thermodynamic models. The adsorption kinetic data were described well by a pseudo second‐order model with R ² of 0.997. There was a negative ΔG (−17.98 kJ mol⁻¹) and positive ΔH (13.58 kJ mol⁻¹). HCl solution (1.0 mol l⁻¹) could achieve an elution rate of 100%. The experimental data were well fitted by the Thomas model with R ² of 0.9826. Copyright © 2016 John Wiley & Sons, Ltd.     

Synthesis,X‐ray characterization and density functional theory studies of N6‐benzyl‐N6‐methyladenine–M(II) complexes (M = Zn,Cd): The prominent role of π–π, C–H···π and anion–π interactions

We report the synthesis and X‐ray characterization of the N⁶‐benzyl‐N⁶‐methyladenine ligand (L) and three metal complexes, namely [Zn(HL)Cl₃]·H₂O ( 1 ), [Cd(HL)₂Cl₄] ( 2 ) and [H₂L]₂[Cd₃(μ‐L)₂(μ‐Cl)₄Cl₆]·3H₂O ( 3 ). Complex 1 consists of the 7H‐adenine tautomer protonated at N3 and coordinated to a tetrahedral Zn(II) metal centre through N9. The octahedral Cd(II) in complex 2 is N⁹‐coordinated to two N⁶‐benzyl‐N⁶‐methyladeninium ligands (7H‐tautomer protonated at N3) that occupy apical positions and four chlorido ligands form the basal plane. Compound 3 corresponds to a trinuclear Cd(II) complex, where the central Cd atom is six‐coordinated to two bridging μ‐L and four bridging μ‐Cl ligands. The other two Cd atoms are six‐coordinated to three terminal chlorido ligands, to two bridging μ‐Cl ligands and to the bridging μ‐L through N3. Essentially, the coordination patterns, degree of protonation and tautomeric forms of the nucleobase dominate the solid‐state architectures of 1 – 3 . Additionally, the hydrogen‐bonding interactions produced by the endocyclic N atoms and NH groups stabilize high‐dimensional‐order supramolecular assemblies. Moreover, energetically strong anion–π and lone pair (lp)–π interactions are important in constructing the final solid‐state architectures in 1 – 3 . We have studied the non‐covalent interactions energetically using density functional theory calculations and rationalized the interactions using molecular electrostatic potential surfaces and Bader's theory of atoms in molecules. We have particularly analysed cooperative lp–π and anion–π interactions in 1 and π⁺–π⁺ interactions in 3 .     

Enhanced antifungal activities of four Zn(II) complexes based on uniconazole

Four Zn(II) complexes, [Zn L ₂(SO₄)]_n ( 1 ), [Zn L ₄(H₂O)₂]?2(NO₃)?4EtOH ( 2 ), [Zn L ₂Cl₂]? L ( 3 ), and [Zn L ₂Br₂]? L ( 4 ) ( L  = uniconazole), were synthesized using a hydrothermal method and characterized by elemental analysis, FT‐IR spectroscopy, and single‐crystal XRD. Complex 1 formed a one‐dimensional polymer chain. However, complexes 2 ‐ 4 were obtained as zero‐dimensional mononuclear coordination compounds. The antifungal activities of these complexes were then evaluated against four selected fungi using the mycelial growth rate method. The resulting data indicate that all complexes show better antifungal activities than their ligands and mixtures. In addition, the interactions between the metal salts of complexes 1 ‐ 4 and uniconazole seem to be synergistic. Furthermore, the polymer chain structure of complex 1 significantly enhanced the bioactivity, especially against Botryosphaeria ribis ( I ). Density functional theory (DFT) calculations were carried out to help explain the enhanced bioactivity after the formation of Zn(II) complexes. The resulting data show that the HOMO–LUMO energy gaps of complexes 1 ‐ 4 (0.0578, 0.0946, 0.1053, and 0.1245 eV) are smaller than that of the free ligand (0.1247 eV) and correlate with the antifungal activity of the zinc complexes.     

反应修饰剂ZnSO4和预处理对苯选择加氢制环己烯Ru-Zn催化剂性能的影响

共沉淀法制备了Ru-Zn催化剂,考察了反应修饰剂ZnSO₄和预处理对苯选择加氢制环己烯Ru-Zn催化剂性能的影响。结果表明,反应修饰剂ZnSO₄可以与Ru-Zn催化剂中助剂ZnO反应生成（Zn（OH）₂）₃（ZnSO₄）（H₂O）盐。随反应修饰剂ZnSO₄浓度增加,（Zn（OH）₂）₃（ZnSO₄）（H₂O）盐量的逐渐增加,Ru-Zn催化剂活性逐渐降低,环己烯选择性逐渐升高。因为（Zn（OH）₂）₃（ZnSO₄）（H₂O）盐中的Zn²⁺可以使Ru变为有利环己烯生成的缺电子的Ru^δ+物种,而且还可以占据不适宜环己烯生成的强Ru活性位。但当反应修饰剂ZnSO₄浓度高于0.41 mol·L^-1后,继续增加ZnSO₄浓度,由于Zn²⁺水解浆液酸性太强,可以溶解部分（Zn（OH）₂）₃（ZnSO₄）（H₂O）盐,Ru-Zn催化剂活性升高,环己烯选择性降低。但环己烯选择性却略微降低,这是由于ZnSO₄溶液中大量的Zn²⁺可以与生成的环己烯形成配合物,稳定生成的环己烯,抑制生成的环己烯再吸附到催化剂表面并加氢生成环己烷。在ZnSO₄最佳浓度0.61 mol·L^-1下对Ru-Zn催化剂预处理15 h,Ru-Zn催化剂中助剂ZnO可以与ZnSO₄完全反应生成（Zn（OH）₂）₃（ZnSO₄）（H₂O）盐,在该催化剂上25 min苯转化68.2%时环己烯选择性和收率分别为80.2%和54.7%。而且该催化剂具有良好的稳定性和重复使用性能。     

One-pot synthesis of selenocarbamates from isocyanates and diselenides using the Zn/AlCl3 system

Several N-alkyl/aryl-Se-alkyl/(aryl)selenocarbamates were prepared from various isocyanates and diselenides by reductive cleavage of Se-Se bond with the Zn/AlCl3 system in dry acetonitrile at 80℃.     

Syntheses and structures of tetranuclear Zn（Ⅱ） complexes with in situ generated macrocyclic Schiff base ligands:Applications in Zn2+ sensing

Three novel Zn（II） complexes,[Zn₄L¹Cl₄]-3H₂O（1）,[Zn₄L²Cl₄]-2DMF（2） and[Zn₄L³Cl₄]H₂O（3）,have been synthesized and structurally characterized.In these complexes,interesting 32-membered dodecadentate macrocyclic ligands were generated in situ by ’2 + 2’ type condensation reactions between a tetraamine and various dialdehydes.All the complexes are isostructurally tetranuclear Zn（Ⅱ） complexes,containing endogenous alkoxo and phenoxo bridges.Applications of the macrocyclic ligands as Zn²⁺ sensors have been investigated.Take H₄L¹ for example,it exhibits a 4-fold fluorescence enhancement upon the addition of 2 equiv.of Zn²⁺ in MeOH.     

Luminescence Study of ZnS Quantum Dots Prepared by Chemical Method

We report synthesis of ZnS quantum dots by chemical method at room temperature. In this technique, ZnS quantum dots are produced by simple chemical reactions where zeolite, acts as matrix, plays the key role in controlling particle growth during synthesis. Quantum dots exhibit luminescence properties such as Zn²⁺ related emission, efficient low voltage electroluminescence, and super linear voltage-brightness EL characteristics. This study demonstrates the technological importance of semiconductor nanosystems prepared by low cost chemical route.     

四溴代对苯二甲酸根及二吡啶基丙烷构筑的锌(Ⅱ)及镉(Ⅱ)配位聚合物的合成及晶体结构

在室温和甲醇/水溶液为溶剂的条件下,以四溴代对苯二甲酸(H2TBTA)及1,3-二(4-吡啶基)丙烷(BPP)为配体合成了[Zn(TBTA)(BPP)]n(1)和[Cd(TBTA)(BPP)2(H2O)2]n(2)2个配位聚合物,对其进行了X-射线单晶衍射、元素分析、红外光谱分析和热重等性质表征。结果表明:配合物1为二维(2D)层状网络结构;配合物2为一维(1D)链状结构;H2TBTA配体中的羧基都采取单齿模式与金属离子配位;配合物中的氢键作用对其结构的稳定性起关键作用。     

CuI/glycerol mediated stereoselective synthesis of 1,2-bis-chalcogen alkenes from terminal alkynes: synthesis of new antioxidants

(E)-1,2-Bis-chalcogen alkenes were stereoselectively prepared in good yields by the addition of diorganyl dichalcogenides to terminal alkynes using CuI/Zn/glycerol as a recyclable catalytic system. The antioxidant activity in vitro of four (E)-1,2-bis-chalcogen alkenes synthesized was evaluated and (E)-1,2-bis-(4-methoxyphenylselanyl)styrene 3b presented excellent activity. The catalytic system used in the synthesis was recovered and used directly up to 5 cycles without loss of activity.