Mixed-Valent Trinuclear CoIII-CoII-CoIII Complex with 1,3-Bis(5-chlorosalicylideneamino)-2-propanol

A mixed-valent trinuclear complex with 1,3-bis(5-chlorosalicylideneamino)-2-propanol (H₃clsalpr) was synthesized, and the crystal structure was determined by the single-crystal X-ray diffraction method at 90 K. The molecule is a trinuclear Co^III-Co^II-Co^III complex with octahedral geometries, having a tetradentate chelate of the Schiff-base ligand, bridging acetate, monodentate acetate coordination to each terminal Co³⁺ ion and four bridging phenoxido-oxygen of two Schiff-base ligands, and two bridging acetate-oxygen atoms for the central Co²⁺ ion. The electronic spectral feature is consistent with the mixed valent Co^III-Co^II-Co^III. Variable-temperature magnetic susceptibility data could be analyzed by consideration of the axial distortion of the central Co²⁺ ion with the parameters Δ = –254 cm⁻¹, λ = –58 cm⁻¹, κ = 0.93, tip = 0.00436 cm³ mol⁻¹, θ = –0.469 K, g_z = 6.90, and g_x = 2.64, in accordance with a large anisotropy. The cyclic voltammogram showed an irreversible reduction wave at approximately −1.2 V·vs. Fc/Fc⁺, assignable to the reduction of the terminal Co³⁺ ions.     

Oxidation of Styrene to Benzaldehyde Catalyzed by Schiff Base Functionalized Triazolylidene Ni(II) Complexes

Four new Schiff base functionalized 1,2,3-triazolylidene nickel complexes, [Ni-(L₁NHC)₂](PF₆)₂; 3, [Ni-(L₂NHC)₂](PF₆)₂; 4, [Ni-(L₃NHC)](PF₆)₂; 7 and [Ni-(L₄NHC)](PF₆)₂; 8, (where L₁NHC = (E)-3-methyl-1-propyl-4-(2-(((2-(pyridin-2-yl)ethyl)imino)methyl)phenyl)-1H-1,2,3-triazol-3-ium hexafluorophosphate(V), 1, L₂NHC = (E)-3-methyl-4-(2-((phenethylimino)methyl)phenyl)-1-propyl-1H-1,2,3-triazol-3-ium hexafluorophosphate(V), 2, L₃NHC = 4,4′-(((1E)-(ethane-1,2-diylbis(azanylylidene))bis(methanylylidene))bis(2,1-phenylene))bis(3-methyl-1-propyl-1H-1,2,3-triazol-3-ium) hexafluorophosphate(V), 5, and L₄NHC = 4,4′-(((1E)-(butane-1,4-diylbis(azanylylidene))bis(methanylylidene))bis(2,1-phenylene))bis(3-methyl-1-propyl-1H-1,2,3-triazol-3-ium) hexafluorophosphate(V), 6), were synthesised and characterised by a variety of spectroscopic methods. Square planar geometry was proposed for all the nickel complexes. The catalytic potential of the complexes was explored in the oxidation of styrene to benzaldehyde, using hydrogen peroxide as a green oxidant in the presence of acetonitrile at 80 °C. All complexes showed good catalytic activity with high selectivity to benzaldehyde. Complex 3 gave a conversion of 88% and a selectivity of 70% to benzaldehyde in 6 h. However, complexes 4 and 7–8 gave lower conversions of 48–74% but with higher (up to 90%) selectivity to benzaldehyde. Results from kinetics studies determined the activation energy for the catalytic oxidation reaction as 65 ± 3 kJ/mol, first order in catalyst and fractional order in the oxidant. Results from UV-visible and CV studies of the catalytic activity of the Ni-triazolylidene complexes on styrene oxidation did not indicate any clear possibility of generation of a Ni(II) to Ni(III) catalytic cycle.     

硅锗合金Seebeck系数影响因素的研究

作为一种洁净能源,硅锗合金的热电转换性能的研究越来越受到人们的重视.本文重点研究了不同Ge浓度的硅锗合金以及Si、Ge单晶在300～1100K温度范围内,Seebeck系数随温度的变化.并对组分相同导电类型不同、晶向不同以及结晶状态不同的样品的Seebeck系数进行了比较.在研究温度区间,Seebeck系数的绝对值大小一般在200～600μV/K之间,随温度不同连续变化.通过对比发现SiGe合金的Seebeck系数大小不仅与Ge的浓度和温度有关,其他因素对其绝对值也有影响,其中晶向最为明显,表现出了明显的各向异性.此外,材料本身的电阻率除了作为一个热电参数影响最优值外,其大小还对Seebeck系数的绝对值有影响,即掺杂济浓度对Seebeck系数的影响.     

Synthesis of Cobalt Bis(Dicarbollide)—Curcumin Conjugates for Potential Use in Boron Neutron Capture Therapy

A series of novel cobalt bis(dicarbollide)—curcumin conjugates were synthesized. Two conjugates were obtained through the nucleophilic ring-opening reaction of the 1,4-dioxane and tetrahydropyran derivatives of cobalt bis(dicarbollide) with the OH group of curcumin, and using two equiv. of the oxonium derivatives, two other conjugates containing two cobalt bis(dicarbollide) units per molecule were obtained. In contrast to curcumin, the conjugates obtained were found to be non-cytotoxic against both tumor and normal cell lines. The analysis of the intracellular accumulation of the conjugates by flow cytometry showed that all cobalt bis(dicarbollide)—curcumin conjugates entered HCT116 colorectal carcinoma cells in a time-dependent manner. New non-cytotoxic conjugates contain a large amount of boron atoms in the biomolecule and can potentially be used for further biological research into boron neutron capture therapy (BNCT).     

A New Supramolecular Tetraruthenated Cobalt (II) Porphyrazine Displaying Outstanding Electrocatalytical Performance in Oxygen Evolution Reaction

A new supramolecular electrocatalyst for Oxygen Evolution Reaction (OER) was synthesized from a central multibridging cobalt tetrapyridylporphyrazine (CoTPyPz) species by attaching four [Ru(bpy)₂Cl]⁺ groups. Both CoTPyPz and the tetraruthenated cobalt porphyrazine species, TRuCoTPyPz, form very homogenous molecular films just by dropcasting their methanol solutions onto GCE electrodes. Such films exhibited low overpotentials for O₂ evolution, e.g., 560 e 340 mV, respectively, displaying high stability, typically exceeding 15 h. The kinetic parameters obtained from the Tafel plots showed that the peripheral complexes are very important for the electrocatalytic activity. Hyperspectral Raman images taken along the electrochemical process demonstrated that the cobalt center is the primary active catalyst site, but its performance is enhanced by the ruthenium complexes, which act as electron-donating groups, in the supramolecular system.     

Removal of Carbamazepine in Aqueous Solution by CoS2/Fe2+/PMS Process

Carbamazepine (CBZ), as a typical pharmaceutical and personal care product (PPCP), cannot be efficiently removed by the conventional drinking water and wastewater treatment process. In this work, the CoS₂/Fe²⁺/PMS process was applied for efficient elimination of CBZ. The CBZ removal efficiency of CoS₂/Fe²⁺/PMS was 2.5 times and 23 times higher than that of CoS₂/PMS and Fe²⁺/PMS, respectively. The intensity of DMPO-HO• and DMPO-SO4•− followed the order of Fe²⁺/PMS < CoS₂/PMS < CoS₂/Fe²⁺/PMS, also suggesting the CoS₂/Fe²⁺/PMS process has the highest oxidation activity. The effects of reaction conditions (e.g., CoS₂ dosage, Fe²⁺ concentration, PMS concentration, initial CBZ concentration, pH, temperature) and water quality parameters (e.g., SO42−, NO3−, H2PO4−, Cl−, NH4+, humic acid) on the degradation of CBZ were also studied. Response surface methodology analysis was carried out to obtain the best conditions for the removal of CBZ, which are: Fe²⁺ = 70 µmol/L, PMS = 240 µmol/L, CoS₂ = 0.59 g/L. The sustainability test demonstrated that the repeated use of CoS₂ for 8 successive cycles resulted in little function decrease (<10%). These findings suggest that CoS₂/Fe²⁺/PMS may be a promising method for advanced treatment of tailwater from sewage treatment plant.     

磁致伸缩材料弱磁场响应特性的实验研究

针对磁致伸缩材料在弱磁场传感器领域的应用需要,采用迈克耳逊干涉原理实验测量了零应力条件下Tb-Dy-Fe材料和Fe-Ga合金的磁场响应灵敏度,以及不同应力下Fe-Ga合金的磁场响应特性和温度响应特性.实验结果表明：在零应力,外加磁场16 mT条件下,Fe-Ga合金的磁场响应灵敏度远高于Tb-Dy-Fe材料,更合适作为弱磁场传感器敏感材料;同时,在1.2 MPa预应力和26 mT偏置磁场下,Fe-Ga合金材料具有较好的磁场响应灵敏度和较大的饱和磁致伸缩系数,因而处在最佳工作状态.所得到的材料的磁场和温度响应曲线可作为弱磁场传感器参量设计的参考依据.     

Obituary: Professor Dr.-Ing. Justus Mühlenpfordt

Abstract

The dose-dependent isotope fractionation during decarboxylation (¹³C/¹²C) amplifies the radiation effect in the relatively low dose range. The fractionation of the nitrogen isotopes during deamination (¹⁵N/¹⁴N) at the dose of 17 Gy was found to be smaller than that of decarboxylation.     

Size-dependent ignition temperature of metallic compounds fabricated by self-propagating high-temperature synthesis

Considering the diffusion reaction at solid interfaces, the ignition temperature of compounds fabricated by self-propagating high-temperature synthesis (SHS) is modelled with the help of size-dependent activation energy. As reactant size decreases, ignition temperature also decreases. This is because of increased contact areas between the reactants and the lowered diffusion barrier, both of which must be calculated specifically for reactants in nanoscale. The model predictions and experimental results are consistent for some metallic compounds.     

Dislocation driven chromium precipitation in Fe-9Cr binary alloy: a positron lifetime study

The influence of initial heat treatment on anomalous Cr precipitation within high temperature solubility region of the Fe–9Cr alloy has been investigated using positron lifetime studies. Air-quenched samples with pre-existing dislocations exhibited a distinct annealing stage in positron lifetime between 800 and 1100?K corresponding to Cr-precipitation. During this stage, Transmission Electron Microscopy showed fine precipitates of average size 4 nm, dispersed throughout the sample and from Energy-dispersive X-ray spectroscopy (EDS) analysis they are found to be Cr-enriched. The presence of dislocations is found to be responsible for Cr precipitation.