Studies on mono- and dinuclear bisoxime copper complexes with different coordination geometries

Two new mono- and dinuclear Cu(II) complexes, namely [CuL¹]·0.5H₂O (1) and [(Cu₂(L²)₂)(DMF)]·0.5DMF (2) (H₂L¹ = 1,2-bis{[(Z)-(3-methyl-5-oxo-1-phenyl-1H-pyrazolidin-4(4H)-yl)(phenyl)]methylene-aminooxy}ethane; H₂L² = 1,3-bis{[(Z)-(3-methyl-5-oxo-1-phenyl-1H-pyrazolidin-4(4H)-yl)(phenyl)] methyleneaminooxy}propane), have been synthesized and characterized by X-ray crystallography. The unit cell of complex 1 contains two crystallographically independent but chemically identical [CuL¹] molecules and one crystalline water molecule, showing a slightly distorted square-planar coordination geometry and forming a wave-like pattern running along the a-axis via hydrogen bonding and π···π stacking interactions. Complex 2 has a dinuclear structure, comprising two Cu(II) atoms, two completely deprotonated phenolate bisoxime (L²)²⁻ moieties (in the form of enol), and both coordinated and hemi-crystalline DMF molecules. Complex 2 has square-planar and square-pyramidal geometries around the two copper centers, whose basic coordination planes are almost perpendicular and form an infinite three-dimensional supramolecular network structure involving intermolecular C–H···N, C–H···O, and C–H···π(Ph) hydrogen bonding and π···π stacking interactions of neighboring pyrazole rings.     

Determinations of Intermediate Neutral Species in Hydrocarbon Discharge Plasma

This work reports laser ionization combined with Time-Of-Flight (TOF) mass spectrometry investigation on intermediate species in the hydrocarbon plasma of atmospheric-pressure fast-flow pulsed dc-discharge. All neutral intermediate species including transient radicals from benzene/Ar discharge have been characterized by a molecular beam sampling combined with TOF mass spectrometry. This shows that with a hydrocarbon gas mixture of 0.3% C₆H₆ in Ar discharge the intermediate species consist of simple radicals (such as C₂, C₅H₅, C₇H₇) and polycyclic organic molecules (C₁₀H₈, C₁₃H₁₀, C₁₄H₁₀). Theoretical studies on total energies and ionization potentials of the intermediate species have been carried out using the hybrid density functional theory. Effect of the ionization potential on mass spectral intensity has been discussed. Based on the observed data, the possible major neutral reaction channels of the plasma chemistry have been discussed. The developed experimental method has implications in volatile organic compounds removing and impurities diagnosis in Tokamak edge-plasma.     

EFFECT OF GAS FLOW RATE ON CRYSTAL STRUCTURES OF ELECTROSPUN AND GAS-JET/ELECTROSPUN POLY(VINYLIDENE FLUORIDE) FIBERS

The effect of gas flow rate on crystal structures of electrospun and gas-jet/electrospun poly(vinylidene fluoride) (PVDF) fibers was investigated.PVDF fibers were prepared by electrospinning and gas-jet/electrospinning of its N,N-dimethylformamide (DMF) solutions.The morphology of the PVDF fibers was investigated by scanning electron microscopy (SEM).With an increase of the gas flow rate,the average diameters of PVDF fibers were decreased.The crystal structures and thermal properties of the PVDF fibers w...     

Planar or quasi-planar octa- and ennea-coordinate aluminum and gallium in boron rings

An ab initio theoretical investigation has been performed on planar or quasi-planar octa-and ennea-coordinate Al and Ga centered in X@B8- and X@B9 (X=Al, Ga). These high symmetry molecular wheels all turned out to be true minima of the systems and σ+π double aromatic in nature, similar to the previously characterized D8h B@B8- both electronically and geometrically. Adiabatic and vertical detachment energies of the anions and the ionization potentials of the neutrals have been calculated to aid their eventua...     

Phase composition and phase transformation in Bi(Sb,Nb,Ta)O4 system

In this work Bi(Sb_xNb_yTa_z)O₄ (x + y + z = 1) samples are prepared using mixed-oxide method. A pseudo-ternary phase diagram of Bi(Sb,Nb,Ta)O₄ system is given below the melting point. It is composed of a monoclinic phase region, an orthorhombic phase region and a monoclinic–orthorhombic co-existing phase region. In the orthorhombic phase region, the transformation from orthorhombic to triclinic phase is found to be sensitive to the composition and sintering temperature. Both the transformation from monoclinic to orthorhombic structure and the transformation from orthorhombic to triclinic structure have been studied by the cell parameters.     

Evaluation of lipid peroxidation inhibition and free radical scavenging abilities of 5,6,7-trimethoxy dihydroflavonols

Four naturally rare 5,6,7-trimethoxy-2,3-cis-dihydroflavonols(3-6) and two 5,6,7-trimethoxy-2,3-trans-dihydroflavonols(7-8) were designed and synthesized.Their antioxidative properties were evaluated by way of examining their scavenging capacities towards DPPH and O_2~(·-) free radicals,as well as by measuring their inhibitory ability against LPO.Both the 2,3-trans and the 2,3- cis conformers exhibited certain quenching abilities to DPPH and O_2~(·-) radicals,while most of the synthetic dihydroflavonols ...     

草酸根掺杂板状溴碘化银颗粒乳剂的增感效应研究

使用反馈式微机控制双注乳化仪,在晶体生长过程中一定时间内,加入一定量的草酸盐,制得了草酸根离子处于晶体颗粒次表面的板状溴碘化银微晶乳剂.对其实验过程的考察和感光性能的测试结果表明:1)草酸根掺杂于次表面的溴碘化银乳剂与未掺杂乳剂相比较,经过化学增感后,或光谱增感后的乳剂,其感光度有明显提高(Sd/S0≥1.5),即具有明显的增感效应;2)无论是经过化学增感,还是经光谱增感后的乳剂,草酸根掺杂溴碘化银颗粒乳剂的灰雾水平都不高.     

Theoretical study on the reaction of the Δ ground state of ZrO with CS2 in the gas phase

The mechanisms for the three products ZrS⁺, and ZrOS⁺ of the title reaction have been studied by using B3LYP/6-311+G* and CCSD(T)/SDD+6-311+G* methods. It is found that both ZrS⁺ and formations involve the same O/S exchange process via a four-center transition state TS12 to form an intermediate IM2. Exception of that IM2 can dissociate into the ZrS⁺ product, a favorable intramolecular rearrangement mechanism associated with the formation has been identified, which explains why ZrS⁺ was excluded as a precusor for the formation and why the lower efficiency of the ZrS⁺ formation was observed in experiment. For the formation of ZrOS⁺, two parallel channels (path A and B) yielding their corresponding product isomer have been identified. Path B involving an insertion–elimination mechanism with a calculated barrier underestimated by ca. 25.0 kJ/mol should be attributed to the threshold of 114.8 ± 12.5 kJ/mol assigned in the experiment. But path A should make some contributions to the formation of ZrOS⁺ at elevated energy.     

Synthesis of phenyl-s-triazine-based copoly(aryl ether)s derived from hydroquinone and resorcinol

A novel series of soluble and heat-resistant copoly(arylene ether phenyl-s-triazine)s (PAEPs) have been prepared for their potent utilities as structural coatings, high-temperature membranes or adhesives. The copolymers have been synthesized via the nucleophilic displacement polymerization of 2,4-bis(4-fluorophenyl)-6-phenyl-1,3,5-triazine (BFPT) with various ratios of hydroquinone (HQ) and resorcinol (RS). A key feature of these copolymers is the incorporation of multiply meta-ether linkages in the polymer chain, which results in an improvement in the solubility of poly(arylene ether phenyl-s-triazine)s in common organic solvents (e.g., N,N’-dimethylacetamide, N,N’-dimethylformamide, N-methyl-2-pyrrolidinone). The new random copolymers exhibit high glass transitions exceeding 241 °C and excellent thermal and thermo-oxidative stabilities associating with decomposition temperatures for 5% mass-loss in excess of 531 °C. These copolymers can be easily cast into tough, clear and creasable films and exhibit good mechanical properties. All copolymers are amorphous except PAEP9010 as evidenced by WAXD. Their solubility increases with an increase in meta-ether linkage content in the polymer backbone, while the crystallinity and the overall thermal stability appear to decrease slightly. This kind of phenyl-s-triazine-based poly(arylene ether) copolymers may be considered a good candidate for using as high-performance polymeric materials.     

Direct electrochemistry and electrocatalysis of hemoglobin in gelatine film modified glassy carbon electrode

Direct electrochemical and electrocatalytic behavior of hemoglobin (Hb) immobilized on glass carbon electrode (GCE) containing gelatine (Gel) films was investigated. The characteristics of Hb/Gel film modified GC electrode were performed by using SEM microscopy, UV-vis spectroscopy and electrochemical methods. The immobilized Hb showed a couple of quasi-reversible redox peak with a formal potential of −0.38 V (versus SCE) in 0.1 M pH 7.0 PBS. The formal potential changed linearly from pH 4.03 to 8.41 with a slope value of −52.0 mV pH⁻¹, which suggested that a proton transfer was accompanied with each electron transfer (ET) in the electrochemical reaction. The Hb/gelatine/GCE displayed a rapid amperometric response to the reduction of H₂O₂ and nitrite.