Study on the Gas Permeability of Nickel(II) Polyurethane Complexes

Ionic polyurethanes (PUs) were prepared from hydroxyl‐terminated polybutadiene (HTPB) and 4,4′‐dicyclohexylmethane diisocyanate (H₁₂MDI) by a two‐stage method. The ionic group was introduced by adding 4,8‐diazaundecanediamide (L‐2,3,2) as the chain extender of which the tertiary amines and carbonyl groups were complexed with nickel ions. It was found that the binding of hard segments and the flexibility of soft segments had subtle effects on the gas permeability. The effects of hard segment content and the amount of nickel ion on the gas permeability and morphological properties were investigated. Fourier transform infrared (FTIR) spectroscopy was utilized to identify the segregation between hard and soft segments and structure change, which affect the transport properties. The hydrogen bonding index (HBI), frequency difference, and shift as a measure of the phase segregation and the average strength of the interpolymer hydrogen bonds were utilized to study the intermolecular interaction and transport property of the prepared PUs. The oxygen and nitrogen permeabilities of membranes were determined by using gas permeability analyzer. The results of FTIR, differential scanning calorimetry and thermogravimetric analysis measurements explain the complexation and, hence, the gas permeability.     

Metal complexes of pyrimidine derived ligands – Syntheses,characterization and X-ray crystal structures of Ni(II), Co(III) and Fe(III) complexes of Schiff base ligands derived from S-methyl/S-benzyl dithiocarbazate and 2-S-methylmercapto-6-methylpyrimidine-4-carbaldehyde

Two new pyrimidine based NNS tridentate Schiff base ligands S-methyl-3-((2-S-methyl-6-methyl-4-pyrimidyl)methyl)dithiocarbazate [HL₁] and S-benzyl-3-((2-S-methyl-6-methyl-4-pyrimidyl)methyl)dithiocarbazate [HL₂] have been synthesised by the 1:1 condensation of 2-S-methylmercapto-6-methylpyrimidine-4-carbaldehyde and S-methyl/S-benzyl dithiocarbazate. A Ni(II) complex of HL₁ and Co(III) and Fe(III) complexes of HL₂ have been prepared and characterized by elemental analyses, molar conductivities, magnetic susceptibilities and spectroscopic studies. All the bis-chelate complexes have a distorted octahedral arrangement with an N₄S₂ chromophore around the central metal ion. Each ligand molecule binds the metal ion using the pyrimidyl and azomethine nitrogen and thiolato sulfur atoms (except in the nickel complex, one ligand molecule uses the thione sulfur in lieu of thiolato sulfur atom). In the Ni(II) complex, one of the ligand molecules behaves as a neutral tridentate and the other molecule functions as a uninegative tridentate, whereas in the Co(III) and Fe(III) complexes, the ligand molecules behave as monoanionic tridentate. All the complexes were analyzed by single crystal X-ray diffraction and significant differences concerning the distortion from an octahedral geometry of the coordination environment were observed.     

Ni/Al2O3催化剂上甲烷部分氧化制合成气反应机理

用变应答／质谱在线检测技术研究了Ｎｉ／Ａｌ２Ｏ３催化剂上甲烷部分氧化制合成气的反应要理，研究结果指出，在常压９７３Ｋ条件下，Ｎｉ／Ａｌ２Ｏ３催化剂上甲烷部分氧化制合成气按直接氧化机理进行，Ｈ２和Ｃ烛甲烷部分氧化的一次产物，其主要反应可表示如下：１．ＣＨ４＋ｘＮｉ－ＮｉｘＣ＋２Ｈ２，２．Ｏ２＋２Ｎｉ－２ＮｉＯ，３．ＮｉｘＣ＋ＮｉＯ－ＣＯ＋（ｘ＋１）Ｎｉ。     

微柱高效液相色谱法测定环境样品中的铁、钴、镍、铜、锌、锰

研究了用 2-(2-喹啉偶氮 )-间苯二酚 (QAR)为柱前衍生试剂 ,以WatersXterraTM RP18(1 .0×5 0mm ,2. 5 μm)微柱为固定相 ,60 %的甲醇 (内含 0 . 5 %的醋酸 )为流动相 ,高效液相色谱分离、二极管矩阵检测器测定铁、钴、镍、铜、锌和锰的方法。根据信噪比 (S N =3 )得各金属离子的检测限分别为 :铁3 μg L、钴 4μg L、镍 2 μg L、铜 4μg L、锌 5 μg L、锰 8μg L ,方法用于环境样品中痕量铁、钴、镍、铜、锌、锰的测定 ,相对标准偏差在 1 . 6%～ 3 . 5 %之间 ,标准回收率为 93 %～ 1 0 7%。     

Versican undergoes specific alterations in the fine molecular structure and organization in human aneurysmal abdominal aortas

Versican is the major matrix proteoglycan in aortic wall and participates in various biological functions of the tissue. In the present study the molecular characteristics of versican isolated from normal human aorta as well as those of versican expressed in aneurysmal aortic tissue were examined. Versican was isolated by combined anion-exchange and gel permeation chromatography and was further characterized by high-performance liquid chromatography, polyacrylamide gel electrophoresis and immunoblotting. In both tissues versican is exclusively substituted with chondroitin sulfate chains, in contrast to other human tissues where both chondroitin and dermatan sulfate chains are attached onto versican core proteins. Except for the significant decrease in the concentration of versican in the aneurysmal tissue, this PG undergoes specific alterations in the aneurysmal tissue. The molecular size of versican isolated from diseased tissue is decreased with a simultaneous increase in the ratio of glycosaminoglycan to protein in this tissue. The latter reflect the extensive fragmentation of versican in the diseased tissue and most probably the generation of shorter peptides enriched to glycosaminoglycan chains. Although the size of chondroitin sulfate chains is identical in both versican preparations, a significant increase in the percentage of 6-sulfated disaccharides is observed in chondroitin sulfate chains of versican in aneurysmal aortas, which is accompanied by decrease in 4-sulfated and non-sulfated units.     

Short synthesis of new salacinol analogues and their evaluation as glycosidase inhibitors

Versatile synthesis of some analogues of the naturally-occurring α-glucosidase inhibitor salacinol (1), involving thioanhydro alditol moieties with erythro, d,l-threo, xylo, ribo, d-arabino and d-manno configurations is described. Nucleophilic attack at the least-hindered carbon atom of an l- or d-protected erythritol cyclic sulfate by the thioanhydro alditol sulfur atom yielded the desired zwitterionic compounds. In addition, the preparation of the cyclic sulfates of 2,4-O-benzylidene-d-erythritol and 2,4-O-isopropylidene-l-erythritol was improved. Enzyme inhibition tests showed that most of the new compounds were weak but specific inhibitors, while good inhibitory activity was found for a six-membered ring analogue (β-glucosidase: K_i=16 μM).     

The study of Ni–Co alloy deposition on iron powder particles in a fluidized bed from sulphate bath

This paper describes a process of electrolytic deposition of nickel–cobalt (Ni–Co) binary alloy on Fe powder. Electrochemical behavior of this binary alloy was studied by cyclic voltammetry with a paraffin impregnated graphite electrode as a working electrode. Deposition of individual metals (Ni, Co), as well as the simultaneous nickel–cobalt co-deposition, was performed in aqueous solutions (Watts-type electrolyte) both with and without Fe powder. Special attention was paid to the influence of suspension density on the electrode process. This density affects on the quality of iron powder electroplating. Preferential deposition of the less noble metal (Co) leading to its higher content in the deposit was observed in contrast to the more noble one (Ni) in spite of higher content of Ni in the plating solution. This anomalous phenomenon–known already for other metals (Zn, Cd, Sn)–has been confirmed and investigated for iron-group metals (Fe, Co, Ni) in this work. Electrolytic deposition of Ni–Co binary alloys, including anomalous behavior is a complicated process. Understanding the anomalous behavior would lead to better control of the deposition process and to explanation of the mechanism of Ni–Co co-deposition.     

Synthesis of a Novel Nickel(II) Complex with Dithiocarbimate from Sulfonamide

Potassium N-4-methylphenylsulfonyldithiocarbimate, K₂(4-CH₃C₆H₄SO₂N=CS₂), reacted with nickel(II) chloride hexahydrate and tetrabutylammonium bromide to form the bis(N-4-methylphenylsulfonyldithiocarbimate)nickelate(II) tetrabutylammonium salt (Bu₄N)₂[Ni(4-CH₃C₆H₄S₂C=NSO₂)₂]. The elemental analyses, IR and UV-Vis data obtained were consistent with the formation of a diamagnetic planar complex. The ¹H NMR and the ¹³C NMR spectra showed the expected signals for the dithiocarbimate moiety and the tetrabutylammonium cation. The single-crystal structure analysis showed that this substance crystallizes in the triclinic space group with a = 10.474(3) Å, b = 10.767(3) Å, c = 13.657(3) Å and = 81.54(2)°, = 80.44(2)°, = 67.63(2)°, V = 1398.5(8) ų, and Z = 2. The nickel atom is coordinated to four sulfur atoms.     

激光热透镜光谱分析法同时测定铜、钴和镍研究

基于2-(5-NO2-吡啶-2-偶氮)-1-羟基-8-氨基萘-3，6-二磺酸与铜(Ⅱ)、钴(Ⅱ)和镍(Ⅱ)反应酸度的差异及热透镜信号强度的加和性，建立了激光热透镜光谱法同时测定铜、钴和镍的新方法。测定铜、钴和镍的线性范围依次为0～200ng/mL、0～200ng/mL和0～100ng/mL，检出限依次为2ng/mL，2．5ng/mL和1ng/mL。方法已用于合成样品及人发样中铜、钴和镍的同时测定。     

Infrared study of νOD modes in isotopically dilute (HDO) kieserite-type compounds MXO4·H2O (M=Mn, Co, Ni, Zn, and X=S, Se) with matrix-isolated M′ and X′O4 guest ions

The hydrogen bond strength in kieserite-type sulfate and selenate monohydrates has been studied by the method of double-matrix spectroscopy. The infrared spectra of isotopically dilute (matrix-isolated HDO molecules) kieserite-type compounds MXO₄·H₂O (M=Mn, Co, Ni, Zn, and X=S, Se) with matrix-isolated X′O₄²⁻ and M′²⁺ guest ions are presented and discussed in the region of the OD stretching modes. The OD frequencies indicate that the compounds under investigation form comparatively strong hydrogen bonds. The frequency shifts of the uncoupled OD stretching modes of the HDO molecules within the isostructural series and those influenced by the guest ions, and the strength of the hydrogen bonds formed, are discussed in terms of the respective O_wO distances, which hint at stronger hydrogen bonds for the sulfate series than for the selenate one by mistake, the larger hydrogen bond acceptor capability of SeO₄²⁻ ions compared to SO₄²⁻ ones, the different metal–water interactions and repulsion potentials of the lattice, and the reorientation of the water molecules caused by the guest ions. The shifts of the OD stretches of the ODOSe′O₃ bonds (Se′O₄²⁻ matrix isolated) to the lower wavenumbers as compared to the parent selenates are caused by the reorientation of the hydrate water molecules and strengthening the hydrogen bond to the stronger acceptor and vice versa. When smaller metal ions having smaller M–OH₂ bond lengths and, hence, stronger synergetic effect replace larger ones, the OD stretches are shifted to lower wavenumbers as compared to those due to the host M–O_wO bonds and vice versa.