Synthesis and neel temperature determination of ferrites from the MO−ZnO−Fe2O3 systems (M=Cu,Co and Ni)

The Curie (Neel) temperature is successfully determined by means of a simple magnetic device attached to the Q Derivatograph (MOM, Hungary), which is widely used in many laboratories. This possibility is demonstrated by a study of ferrite materials with general formula M_xZn_1?xFe₂O₄ (M=Cu, Co and Ni;x=0.0; 0.2; 0.4; 0.5; 0.6; 0.8; 1.0). X-ray phase analysis, Mössbauer spectroscopy and microscopic examinations revealed that the obtained ferrites are monophase samples. The mixed ferrites possess more strongly expressed magnetic properties than those of the individual ferrites; the maximum magnetic interaction in these ferrites is observed at different zinc contents.     

活性位高度暴露的钴/氮/碳电催化剂的构建及氧还原性能研究

金属/氮/碳催化剂（M/N/C，M=Fe、Co等）是最有发展前景的非贵金属电催化剂之一，其性能依赖于催化剂表面的活性物种密度.通过常规的热解含氮前驱物与金属盐的方法制得的催化剂往往存在金属活性物种被包埋而不能有效利用的缺点.考虑到石墨相氮化碳（g-C₃N₄）富含类吡啶氮和亚纳米孔腔结构，将g-C₃N₄包覆在高导电性碳纳米笼（hCNC）表面，进而利用表层g-C₃N₄的配位和限域作用锚定大量Co²⁺离子，获得的Co/g-C₃N₄/hCNC复合物经热解后形成了活性位高度暴露、导电性好、孔结构丰富的Co/N/C催化剂.800℃热解得到的最优化催化剂在碱性介质中展现出优异氧还原活性，其起始电位（0.97 V）与商业Pt/C催化剂相当，且抗甲醇干扰性能和稳定性优异.此项研究提供了一种构建具有高度暴露活性位的M/N/C催化剂的有效策略.     

Synthesis and biological evaluation of 3-amino-propan-1-ol based poly(ether imine) dendrimers

A general synthetic strategy for the rapid construction of poly(ether imine) dendrons and dendrimers with a nitrogen core, originating from 3-amino-propan-1-ol, is described. A new trifunctional monomer, namely, 3-[bis-(3-hydroxypropyl)amino]propan-1-ol, was used in a divergent synthesis of dendrimers up to the third generation. This method permitted installation of, either alcohol, amine, nitrile, ester or carboxylic acid groups at the peripheries the dendrimers. Cytotoxicity studies on water-soluble carboxylic acid terminated dendrimers were conducted and these studies revealed that poly(ether imine) dendrimers were non-toxic. These results illustrate that poly(ether imine) dendrimers are useful for biological studies.     

Hydrothermal Syntheses and Structural Characterization of Two Novel Arsenic–Vanadium Clusters: [Co(2,2′-bpy)3]2[As8V14O42(H2O)]·3H2O and [2,2′-bpy][Ni(2,2′-bpy)3]2[As8V14O42(H2O)]·3H2O

Two new arsenic–vanadium clusters, [Co(2,2- bpy)₃]₂[As₈V₁₄O₄₂(H₂O)] · 3H₂O (1), [2,2-bpy][Ni(2,2-bpy)₃]₂[As₈V₁₄O₄₂(H₂O)] · 3H₂O (2) (2,2-bpy=2,2-bipyridine), have been hydrothermally synthesized and characterized by IR, elemental analysis, UV–VIS, EPR, TGA, XPS, and single crystal X-ray diffraction analysis. Crystal data: 1, triclinic, P1, a=14.368(3) Å, b=16.753(3) Å, c=24.632(5) Å, =94.15(3)°, =93.16(3)°, =113.05(3)°, Z=2; 2, monoclinic, P2₁/c, a= 30.2150(4) Å, b=14.0690(3) Å, c=26.0536(3) Å, =106.8960(10)°, Z=4. X-ray crystallographic studies showed that crystals 1 and 2 are both composed of discrete cluster anion [As₈V₁₄O₄₂(H₂O)]^4– and transition metal coordination complexes [M(2,2-bpy)₃]²⁺ (M=Co or Ni). Interestingly, compound 2 contains another neutral organic space filler of 2,2-bpy. To the best of our knowledge, compounds 1 and 2 are the first examples of structurally characterized vanadium/2,2-bpy/arsenate polyoxometallates.     

Cobalt Ion Incorporation into Periodic Mesoporous Organosilica Materials Synthesized by Co-condensation of 1,2-Bistrimethoxysilylethane with 3-Glycidoxypropyltriethoxysilane

Bifunctional periodic mesoporous organosilica materials with and without cobalt ion incorporation were synthesized by co-condensation of 1,2-bistrimethoxysilylethane (BTME) with 3-glycidoxypropyltriethoxysilane (GPTS) in the presence of cetyltrimethylammonium bromide. Nitrogen gas adsorption on samples with varying ratios of BTME:GPTS revealed that increasing the amount of GPTS affects pore size, surface area and pore volume as well as shapes of the isotherms and hysteresis loops. The hysteresis loops of the Type IV isotherms obtained for GPTS-modified ethane silica materials (without cobalt ion) change from Type H3 to Type H4 with increasing GPTS content. There is a tendency for pore sizes to change from mesopore to micropore when the amount of GPTS is increased. Isotherms of cobalt ion incorporated GPTS-modified ethane silica materials change from Type IV to Type I with increasing GPTS content. The surface area, pore volume and pore diameter decrease with increasing loading of GPTS as well as after cobalt ion incorporation. Thermogravimetric analysis and differential thermal analysis show that the surfactant is removed by solvent extraction. Cobalt ion incorporation is confirmed by powder X-ray diffraction and Raman spectroscopy.     

系数倍率法同时测定铁钴镍三组分的研究

本文运用了在乙酸缓冲液中铁，钴，镍与亚硝基红盐（ＮＲＳ）生成有色配合物光吸收的差异，分别采用系数倍率法消除相互之间的干扰取得了满意的结果。     

CoI- and Co0-bipyridine complexes obtained by reduction of CoBr2bpy: electrochemical behaviour and investigation of their reactions with aromatic halides and vinylic acetates

The electrochemical behaviour of CoBr(2)bpy (bpy=2,2'-bipyridine) catalyst precursor in acetonitrile has been studied, revealing its possible reduction into the corresponding Co(I) and Co(0) complexes. These low-valent cobalt species appear to be stable on the time scale of cyclic voltammetry. In the presence of aromatic halides, both complexes undergo oxidative addition, the latter Co(0) species allowing the activation of poorly reactive aromatic chlorides. The arylcobalt(III) and arylcobalt(II) obtained are reduced at the same potential as the original Co(II) and Co(I) complexes, respectively, resulting in the observation of overall ECE mechanisms in both cases. The electrochemical study shows that vinylic acetates competitively react with electrogenerated Co(0) species, leading to a labile complex. Preparative scale electrolyses carried out from solutions containing aromatic halides (ArX), vinyl acetate (vinylOAc) and a catalytic amount of CoBr(2)bpy lead to a mixture of biaryl (Ar-Ar) and arene (ArH) as long as the potential is set on the plateau of the Co(II) right arrow over left arrow Co(I) reduction wave. The coupling product (Ar-vinyl) is formed only if the electrolysis is performed on the plateau of the Co(I)/Co(0) reduction wave. A mechanism is proposed for the overall cobalt-catalyzed coupling reaction between aromatic halides and allylic acetates.     

Crystal Structure and Ethylene Oligomerization Catalytic Activity of {2-Carbethoxy-6-[1-[（2,6-diethylphenyl）imino]ethyl]pyridine}CoCl2

The unsymmetric precursor ethyl 6-acetylpyridine-2-carboxylate （4） was synthesized from 2,6-dimethylpyridine （1）. On the basis of this precursor, a new mono（imino）pyridine ligand （5） and the corresponding Co（Ⅱ） complex {2-carbethoxy-6-[1-[（2,6-diethylphenyl）imino]ethyl]pyridine}CoCl2 （6） were prepared. The crystal structure of complex indicates that the 2-carbethoxy-6-iminopyridine is coordinated to the cobalt as a tridentate ligand using [N, N, O] atoms, and the coordination geometry of the central cobalt is a distorted trigonal bipyramid, with the pyridyl nitrogen atom and the two chlorine atoms forming the equatorial plane. Being applied to the ethylene oligomedzation, this cobalt complex shows catalytic activity of 1.820× 10^4 g/mol-Cooh at 101325 Pa of ethylene at 15.5℃ for 1 h, when 1000 equiv, of methylaluminoxane （MAO） is employed as the cocatalyst.     

Investigation of the metal binding site in methionine aminopeptidase by density functional theory

All methionine aminopeptidases exhibit the same conserved metal binding site. The structure of this site with either Co²⁺ions or Zn²⁺ions was investigated using density functional theory. The calculations showed that the structure of the site was not influenced by the identity of the metal ions. This was the case for both of the systems studied; one based on the X-ray structure of the human methionine aminopeptidase type 2 (hMetAP-2) and the other based on the X-ray structure of the E. colimethionine aminopeptidase type 1 (eMetAP-1). Another important structural issue is the identity of the bridging oxygen, which is part of either a water molecule or a hydroxide ion. Within the site of hMetAP-2 the results strongly indicate that a hydroxide ion bridges the metal ions. By contrast, the nature of the oxygen bridging the metal ions within the metal binding site of eMetAP-1 cannot be determined based on the results here, due to the similar structural results obtained with a bridging water molecule and a bridging hydroxide ion.     

Effect of film thickness on the electro-reduction of molecular oxygen on electropolymerized cobalt tetra-aminophthalocyanine films

We studied the electrocatalytic activity of cobalt tetra-aminophthalocyanine (CoTAPc) for the reduction of molecular oxygen (O₂) on adsorbed monomeric and on electropolymerized films of different thicknesses on glassy carbon (GC) electrode. The polymeric films, denoted poly-CoTAPc, were first characterized by electrochemical impedance spectroscopy and it appears that the types of phenomena revealed to be occurring depend less on the film thickness in basic than in acid media. For O₂ reduction, the results showed that poly-CoTAPc is more active than the monomeric CoTAPc adsorbed on GC. Indeed, rotating ring-disk electrode data showed that polymeric CoTAPc promotes the four-electron reduction of O₂ to water in parallel to a two-electron reduction to give peroxide. On monomeric and thin films of poly-CoTAPc, a two-electron reduction mechanism predominates. In basic media the activity increases very slightly with thickness, whereas in acid media this increase is more pronounced. This parallels the observed behavior revealed by electrochemical impedance spectroscopy.