A tetranuclear nickel(II) complex for water oxidation: Meeting new challenges

Ni complexes are promising catalysts for water splitting. Herein, a tetranuclear nickel(II) complex with bis-[(E)-N′-(1-(pyridin-2-yl)ethylidene)]carbohydrazide (HL), was synthesized and characterized by spectroscopic methods and single crystal X-ray analysis. The complex is a tetranuclear complex and the ligands are coordinated to the metal ions in the mono-negative form, (L)^- to form a tetranuclear [NiL]₄⁴⁺ unit. Each Ni(II) ion is six-coordinated by pyridine nitrogen, azomethine nitrogen and oxygen atoms of two perpendicular carbohydrazone ligands in the mer configuration. The complex was studied as a water-oxidizing catalyst. In the next step, the role of the Ni-based compound for water oxidation on the surface of fluorine doped tin oxide as one of the true catalysts was investigated by scanning transmission electron microscopy, scanning transmission electron microscopy, spectroelectrochemistry, and electrochemistry. The electrode after water oxidation by the complex was studied and a relation between the decomposition of the Ni complex and water-oxidation reaction was proposed. The experiments show that under water-oxidation condition in the presence of the complex, a Ni-based compound on the electrode is a candidate as a contributor to the observed catalysis.     

大化甲醇项目25500Nm3/h空分氩系统调试总结

介绍了大化甲醇装置空分氩系统调试经过,并进行了经验总结.     

Multifunctional Composites of Chiral Valine Derivative Schiff Base Cu(II) Complexes and TiO2

We have prepared four new Cu(II) complexes containing valine moieties with imidazole ligands at the fourth coordination sites and examined their photo-induced reactions with TiO₂ in order of understanding the reaction mechanisms. Under a nitrogen atmosphere, the intermolecular electron transfer reactions (essentially supramolecular interactions) of these systems, which resulted in the reduction of Cu(II) species to Cu(I) ones, occurred after UV light irradiation. In this study, we have investigated the conditions of the redox reactions in view of substituent effects of aldehyde moieties. The results of cyclic voltammetry (CV) on an rotating ring-disk electrode (RRDE) suggested that the substitution effects and redox potentials were correlated. Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations were also performed to simulate the UV–Vis and circular dichroism (CD) spectra; the results revealed a reasonably good correlation between the substituent effects and the highest occupied molecular orbitals and the lowest unoccupied molecular orbitals (HOMO-LUMO) gaps associated with the most intense transition bands. In addition, we summarized the substitution effects of Cu(II) complexes for their corresponding UV light-induced reactions.     

锦屏二级水电站地下洞室开挖围岩卸荷效应分析及工程应用

根据工程地质条件,基于卸荷岩体理论对锦屏二级水电站地下洞室进行开挖数值模拟计算,以桩号厂右0+000.0剖面为主要研究对象,结合变形监测资料进行卸荷区的划分,分析围岩在开挖、卸荷、加固各工况下的塑性区演化过程。数值计算结果表明,监测点的监测位移与计算位移吻合情况较好。以主厂房第二步开挖全过程为例,可知开挖工况下围岩强卸荷区出现的塑性区在卸荷工况下进一步扩大,而在锚索加固完成后,塑性区基本消失。这说明强弱卸荷区的划分较为合理,建立的模型适当,设计锚固方案有效可行。     

Synthesis of Ion Imprinted Polymers by Copolymerization of Zn(II) and Al(III)8-hydroxy Quinolone Complexes with Divinylbenzene and Methacryclic Acid

In this research work, Zinc(II) and Aluminum(III)-IIP's were synthesized by optimizing the amount of methacrylic acid as monomer, divinylbenzene as cross-linker. The IIP's were functionalized with 8-hydroxy quinolone complexes of the two metal ions under thermal conditions by copolymerization with monomer and cross-linker. The IIP's and Non-IIP's were characterized using FT-IR, TGA, and SEM analysis. A quite remarkable difference in the size was observed of the polymers (Zn(II) 1.0 µm and Al(III) 0.1 µm). A stronger affinity was observed with IIP in comparison with Non-IIP at pH 3.1 and 4.5 for Zn(II) and Al(III) ions on their respective polymers.     

Detailed Insight into the Interaction of Bicyclic Somatostatin Analogue with Cu(II) Ions

Somatostatin analogues are useful pharmaceuticals in peptide receptor radionuclide therapy. In previous studies, we analyzed a new bicyclic somatostatin analogue (BCS) in connection with Cu(II) ions. Two characteristic sites were present in the peptide chain: the receptor- and the metal-binding site. We have already shown that this ligand can form very stable imidazole complexes with the metal ion. In this work, our aim was to characterize the intramolecular interaction that occurs in the peptide molecule. Therefore, we analyzed the coordination abilities of two cyclic ligands, i.e., P1 only with the metal binding site and P2 with both sites, but without the disulfide bond. Furthermore, we used magnetic circular dichroism (MCD) spectroscopy to better understand the coordination process. We applied this method to analyze spectra of P1, P2, and BCS, which we have described previously. Additionally, we analyzed the MCD spectra of P3 ligand, which has only the receptor binding site in its structure. We have unequivocally shown that the presence of the Phe-Trp-Lys-Thr motif and the disulfide bond significantly increases the metal binding efficiency.