Four Zn(II)/Cd(II)-3-amino-1,2,4-triazolate frameworks constructed by in situ metal/ligand reactions: Structures and fluorescent properties

Four Cd(II) and Zn(II) complexes with the in situ-generated ligand of 3-amino-1,2,4-triazolate (AmTAZ⁻) were isolated from the solvothermal reactions of the corresponding Cd(II) or Zn(II) salts with 5-amino-1H-1,2,4-triazole-3-carboxylic acid (AmTAZAc). Their structures were determined by single-crystal X-ray diffraction analysis. [Zn(AmTAZ)(CH₃COO)] (1) presents a two-dimensional framework constructed from Zn(II) ions and μ₃-AmTAZ⁻ ligands. A remarkable feature of [Zn₄(AmTAZ)₄(SO₄)(OH)(C₂O₄)_0.5]·2H₂O (2) is the construction of the building units of octagonal cylinders which interact with each other by sharing one face or overlapping, resulting in the formation of a three-dimensional framework with three kinds of 1D channels. [Cd(AmTAZ)Br] (3) crystallizes in a chiral space group P2₁2₁2₁, giving a homochiral three-dimensional framework with two types of helical channels (left- and right-handed). Different from the others, the 3-amino-1,2,4-triazole molecules in [Cd(AmTAZH)SO₄] (4) behave as neutral μ₂-2,4-bridges to connect the two-dimensional CdSO₄ sheets into a three-dimensional framework. Of all, 2 and 3 display different fluorescent properties probably due to different metal ions, coordination environments and structural topologies.     

Solvothermal synthesis and removal capacity for hydrogen chloride gas of Zn(OH)(NO3) with a rare (10,3)-d net

A basic zinc nitrate, [Zn(OH)(NO₃)]_n with a novel framework reported herein is prepared by solvothermal synthesis, and holds a rare three-dimensional (10,3)-d net called by Wells. It crystallizes in orthorhombic, space group, Pna2₁ (No. 33), , , , Z=4, , , , 3.49<θ<27.51, , R₁=0.029, wR₂=0.0773 for 697 (I>2σ(I)) of 1728 [R_(int)=0.0246] unique reflections and 59 parameters. GOF=1.073. Interestingly this basic zinc nitrate, [Zn(OH)(NO₃)]_n behaves well at removal capacity for hydrogen chloride gas, 20.3 g HCl/100 g, and its framework is not destroyed yet. This adsorption character may be useful for the removal of toxic gases in the environment.     

Fabrication of CdS Nanorods in PVP Fiber Matrices by Electrospinning

Summary: A controlled fabrication of rod‐like nanostructures of cadmium sulfide (CdS) incorporated into polymer fiber matrices has been developed by an electrospinning method. Here, poly(vinyl pyrrolidone) (PVP) was used as a polymer capping reagent, utilizing the interactions of cadmium ions with the carbonyl groups in the PVP molecules. The formation of CdS nanorods inside the PVP was carried out via the reaction of Cd²⁺ with H₂S. SEM images showed that the electrospun films of PVP/CdS are composed of fibers with a diameter between 100 and 900 nm. TEM proved that most of the CdS nanorods are incorporated in the PVP fibrous film. The diameter of the rod is about 50 nm and the length is from 100 to 300 nm.

TEM image of the CdS nanorods formed in the PVP fibrous film.     

Electrochemical polarisation and galvanic couple behaviour of the primary phase of 55% Al–Zn coating investigated using band microelectrodes (BME) and band microelectrode arrays

Electrochemical polarisation experiments have shown that anodic dissolution processes on Al–40% Zn alloys are significantly enhanced in chloride compared to sulfate-based electrolytes. The aluminium content of the alloys allowed passive behaviour to be observed in sulfate electrolyte even in the presence of zinc-rich precipitates on the surface. Electrolyte pH affected cathodic processes, which was attributed to the rate of proton reduction and the passivity of the surface. Monitoring the OCP of the alloy band during polarisation of neighbouring zinc electrodes in band microelectrode (BME) arrays showed that generation of alkaline pH at the zinc electrodes affected the OCP of the alloy when the inter-electrode spacing was 10, 50, and 200 μm. Where elements of a BME array were close enough to interact via mass transport, the overall galvanic behaviour of the cell was found to be anodic or cathodic, whereas the alloy was consistently cathodic with respect to zinc in galvanic cells at larger separations. Dedicated to the 80th birthday of Keith B. Oldham.     

meso-四-(对甲氧基)苯基卟啉和meso-四-(对甲氧基)苯基卟啉的电化学性质

锌卟啉配合物;合成;meso-四-(对甲氧基)苯基卟啉和meso-四-(对甲氧基)苯基卟啉的电化学性质     

Preparing Nano-ZnS by Solid State Reaction at Room Temperature

Solid-state reaction has been studied for a long time1-3. In recent years, some researches have been focused on the preparation of coordination compounds at low temperatures or even at room temperature4-5. In this letter, preparation of ZnS nanoparticles by using solid state reaction at room temperature is reported.ZnS nanoparticles were prepared as follows: Zn(CH3COO)2 and Na2S?9H2O, in equal molar ratio, were ground in agate mortar. After 20 minutes, the powder was washed by water and …     

表面过剩S2-对CdS光催化的影响与带位匹配

用ESR方法研究了硫化镉超微粒子表面被不同浓度的过剩硫离子S2－改性后对其光诱导电子转移及底物的氧化还原反应进程的影响.结果表明,在较高浓度下光还原反应易于进行.若所用底物的氧化还原电位E0为负值,在无过剩S2－存在及低浓度S2－环境中不发生光还原反应,但却可在高浓度S2－环境发生反应; 若底物的E0为正值,则在无硫离子及较低硫离子浓度下能够发生的光氧化反应,在高浓度时则被完全抑止.这是由于表面过剩S2－的作用,改变了底物的氧化还原电位与半导体超细微粒带隙间的匹配关系.根据Langmuir 等温吸附模型,进一步导出了修饰物的浓度c与平带电位负移值间的关系表达式ΔEfb=Δ Kc/(1＋Kc).可以合理解释修饰物 S2－的浓度越高,Efb负移越大,越有利于光还原反应的实验事实.因此根据需要,适当地选择修饰物并控制浓度,使带隙位置与底物氧化还原电位间能有合适的匹配,有助于调节光化学反应的选择性与方向.     

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.     

The enhanced biological activities of three Zn (II) complexes based on different 1,2,4‐triazole fungicides

In order to screen effective fungicides, three Zn (II) complexes, [Zn L ¹ ₄ (NO₃)₂]·2H₂O·2EtOH ( 1 ), [Zn L ² ₄ (NO₃)₂] ( 2 ), and [Zn L ³ ₄ (DMF)₂](NO₃)₂ ( 3 ), ( L ¹  = paclobutrazol, L ²  = diniconazole, and L ³  = hexaconazole), were synthesized and characterized by elemental analysis, FT‐IR spectroscopy, and single‐crystal XRD. 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 the complexes show the enhanced antifungal activities than the corresponding ligand and mixtures. And, the interactions between the metal salt and ligands in the three complexes seem to be synergistic. According to the study of the influence of the structures on the activity, complex 2 with C=C linkage and 2,4‐dichlorophenyl moieties enhances the bioactivity significantly, especially against Wheat gibberellic ( II ). Density functional theory (DFT) calculations were carried out to help explain the enhanced bioactivity of the Zn (II) complexes. Meanwhile, all complexes are excellent grow‐regulators, especially complex 3 . The resulting data show that the complexes based on triazole fungicides have the potential applications in agriculture.     

Developing a robust LC–MS/MS method to quantify Zn‐DTPA,a zinc chelate in human plasma and urine

Quantitation of Zn‐DTPA (zinc diethylenetriamene pentaacetate, a metal chelate) in complex biological matrix is extremely challenging on account of its special physiochemical properties. This study aimed to develop a robust and specific liquid chromatography–tandem mass spectrometry (LC–MS/MS) method for determination of Zn‐DTPA in human plasma and urine. The purified samples were separated on Proteonavi (250 × 4.6 mm, 5 μm; Shiseido, Ginza, Tokyo, Japan) and a C₁₈ guard column. The mobile phase consisted of methanol–2 mm ammonium formate (pH 6.3)–ammonia solution (50:50:0.015, v/v/v), flow rate 0.45 mL/min. The linear concentration ranges of the calibration curves for Zn‐DTPA were 1–100 μg/mL in plasma and 10–2000 μg/mL in urine. The intra‐ and inter‐day precisions for quality control (QC) samples were from 1.8 to 14.6% for Zn‐DTPA and the accuracies for QC samples were from −4.8 to 8.2%. This method was fully validated and successfully applied to the quantitation of Zn‐DTPA in plasma and urine samples of a healthy male volunteer after intravenous infusion administration of Zn‐DTPA. The result showed that the concentration of Zn‐DTPA in urine was about 20 times that in plasma, and Zn‐DTPA was completely (94.7%) excreted through urine in human.