Synthesis and characterization of VO–vanillin complex immobilized on MCM-41 and its facile catalytic application in the sulfoxidation reaction,and synthesis of 2,3-dihydroquinazolin-4(1H)-ones and disulfides in green media

In this work, a vanillin complex is immobilized onto MCM-41 and characterized by FT-IR, X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, thermogravimetric analysis, and BET techniques. This supported Schiff base complex was found to be an efficient and recoverable catalyst for the chemoselective oxidation of sulfides into sulfoxides and thiols into their corresponding disulfides (using hydrogen peroxide as a green oxidant) and also a suitable catalyst for the preparation of 2,3-dihydroquinazolin-4(1H)-one derivatives in water at 90°C. Using this protocol, we show that a variety of disulfides, sulfoxides, and 2,3-dihydroquinazolin-4(1H)-one derivatives can be synthesized in green conditions. The catalyst can be recovered and recycled for further reactions without appreciable loss of catalytic performance.     

Functional zinc(II) phthalocyanines bearing Schiff base complexes as oxidation catalysts for bleaching systems

Oxidation catalysis is used to increase the performance of hydrogen peroxide in laundry bleach applications. Bleach catalysts provide cost‐effective, energy‐saving and environmentally friendly bleach systems yielding perfect stain removal at lower temperatures. This comparative study is based on the synthesis of bis[bis(salicylhydrazonephenoxy)manganese(III)] phthalocyaninatozinc(II) ( 2 ), bis[bis(salicylhydrazonephenoxy)cobalt(III)] phthalocyaninatozinc(II) ( 3 ) and bis[bis(salicylhydrazonephenoxy)iron(III)] phthalocyaninatozinc(II) ( 4 ) as tri‐nuclear complexes consisting of two Schiff base complexes substituting a zinc phthalocyanine. Complexion on the periphery to obtain complexes 2 , 3 , 4 was performed through the reaction of a Schiff base‐substituted phthalocyanine using MnCl₂?4H₂O, CoCl₂?6H₂O or FeCl₃?6H₂O salts in basic condition in dimethylformamide. Fourier transform infrared, ¹H NMR, ¹³C NMR, UV–visible, inductively coupled plasma optical emission and mass spectra were applied to characterize the prepared compounds. The bleach performances of the three phthalocyanine compounds 2 , 3 , 4 were examined by the degradation of morin as hydrophilic dye. The degradation progress in the presence of catalysts 2 , 3 , 4 /H₂O₂ combination in aqueous solution was investigated using an online spectrophotometric method. It was found that the catalysts 2 , 3 , 4 exhibited better bleaching performance at 25 °C than tetraactylethylethylenediamine as bleach activator used in powder detergent formulations for stain removal. Copyright © 2015 John Wiley & Sons, Ltd.     

Formation of low-temperature deformation-induced segregations of nickel in Fe–Ni-based austenitic alloys

ABSTRACT

The authors present the results of an investigation in Fe–Ni-Cr austenitic alloys of the low-temperature deformation-induced segregations of nickel that form in the micro regions being (i) located close to grain- and subgrain boundaries and (ii) characteristic of the concentration and magnetic inhomogeneities indicated by the appearance of a dark diffraction contrast at the electron diffraction patterns taken from these regions typical (at the same time) of an enhanced value of Curie temperature. The observed effects were connected with the micro distortions caused by the local change of lattice parameter because of an increase in nickel concentration, as well as in the result of a magnetostriction dilatation. Using methods of the X-ray energy dispersive spectroscopy (XEDS) and atomic-probe body-section radiography (tomography – APT) has made it possible to determine the borders of those regions of austenite that were characteristic of an enhanced concentration of nickel in the fields of the localisation of a deformation-induced segregation of nickel in the vicinity of grain (subgrain) boundaries of austenitic alloys of the types Fe–13Cr–30Ni and Fe–37Ni–3Ti.     

Functionalized Silver-Ion-Mediated α-dC/β-dC Hybrid Base Pairs with Exceptional Stability: α-d-5-Iodo-2′-Deoxycytidine and Its Octadiynyl Derivative in Metal DNA

Silver-mediated α-dC–Ag⁺–β-dC hybrid base pairs decorated with 5-iodo- or 5-octadiynyl residues are well accommodated in duplex DNA. A strong T_m increase and favorable thermodynamic data for duplex DNA were observed after addition of silver ions. The phenomenon is particularly obvious when both nucleobases of the base pairs are functionalized. Neither the position of the base pair, nor the type of 5-substituent had a negative influence. On the contrary, functionalization of conventional silver-mediated β-dC–Ag⁺–β-dC homo base pairs showed a negative impact induced by the bulky substituents. To this end, cytosine modified 12-mer oligodeoxynucleotides were prepared by solid-phase synthesis employing new α-anomeric 2′-deoxycytidine phosphoramidites. A multigram scale synthesis was developed for 5-iodo-α-d -2′-deoxycytidine ( 1 ) employing the direct glycosylation of cytosine with Hoffer's α-d -halogenose followed by separation of anomeric DMT nucleosides. Regarding base-pair stability and functionalization silver-mediated α/β-dC hybrid base pairs were found to be superior to β/β-dC homo pairs. According to their extraordinary properties, they might find applications in DNA diagnostics, material science, or nanotechnology.     

Cyanide-Free One-Pot Synthesis of Methacrylic Esters from Acetone

Methacrylic esters, represented by methyl methacrylate (MMA), are widely used as commodity chemicals. Here, the one-pot synthesis of methacrylic esters from acetone, a haloform and alcohols in the presence of an organic base is described. Using DBU as the organic base for the reaction of acetone, chloroform and methanol in acetonitrile afforded MMA in 66 % yield. When the solvent was replaced by benzonitrile, the product MMA was successfully purified by distillation. Applicability of this process to various alcohols was also investigated to show ethyl, phenyl, CF₃CH₂, and n-C₆F₁₃CH₂CH₂ esters were obtained in moderate yields. The use of bromoform instead of chloroform resulted in the improvement of the yield, for example, methyl and n-C₆F₁₃CH₂CH₂ esters up to 81 and 70 %, respectively. The reaction with deuterated starting materials acetone-d₆ and MeOH-d₄, with DBU in acetonitrile afforded deuterated MMA (MMA-d₈) in 70 % yield.     

采用多元化的教学手段,提高物理人才的综合素质——南开大学物理学基础科学人才培养基地建设经验介绍

介绍了南开大学国家物理学基础科学研究人才培养基地在十多年的建设中,通过多元化的教学手段提高学生的学习自主性,通过加强科研训练提高物理人才综合素质的经验和取得的成果.     

93W合金有关力学参量的综合选评

 对93W合金材料进行了超声测量实验，并结合原有的超声测量结果进行了分析比较，提出了可以直接用冲击波速度关系式的三个系数c₀ 、λ和λ′来对钨合金的有关力学参量，如G₀、K₀、G₀′、K₀′等进行综合选评的方法。得到了一组对93W合金较为合理的力学参量推荐值。     

Chronoamperometric studies in an ammonia citrate electrolyte for the deposition of a nickel-molybdenum alloy

Dependences of the current and the chemical composition of cathodic deposits on the electrolysis time are studied in an ammonia-citrate electrolyte for the deposition of a nickel-molybdenum alloy in potentiostatic conditions. At potentials less negative than ?0.93 V, no nickel-molybdenum alloy deposition occurs and in the course of electrolysis there is observed a decrease in the current, which is connected with the blocking of the electrode surface by the formed molybdenum oxides. In the region of potentials of deposition of a nickel-molybdenum alloy there is realized the following shape of a time dependence of the current. Within the first few seconds of the electrolysis process, the current somewhat decreases. Then there occurs its increase, which is connected with the alloy deposition on the cathode. In the course of electrolysis there occurs a decrease in the molybdenum content in the cathodic deposit.     

SiOx纳米管的制备及其发光特性

以液态金属镓为媒介,利用热蒸发法合成大量非晶SiOx纳米管,这些纳米管管径均匀分布,平均约80 nm,长度大于10μm,且管内外径比例较小．分析发现,在实验过程中,熔入金属镓液滴中的硅元素和氧元素结合并从液滴的表面饱和析出,形成以镓为中心的非晶SiOx纳米管状结构．在室温中,利用260 nm的激发光源激发SiOx纳米管,发现在蓝光波段附近发出强而稳定的PL谱线,这可能与样品中的氧缺陷和空位有关．     

基于MATLAB(SIMULINK)的电弧炉电极调节系统FUZZY-PD控制器的仿真

介绍了采用MATLAB V5.2提供的模糊逻辑工具箱来设计研究电孤纺电极调节系统中的模糊－－PD控制器，讨论了在SIMULINK环境下模糊－PD控制器的参数自调速原理、结构、建立模糊控制规则库和模糊推论方法，并给出仿真结果与结论。