含氟苯硼酸的合成及应用研究进展

含氟苯硼酸是一种重要的有机合成中间体, 在有机合成中应用相当广泛. 综述了近年来含氟苯硼酸的合成及应用方面的重要研究进展.     

Photolysis of organic pollutants in wastewater with 206 nm UV irradiation

A new-type UV light source(206 nm) was explored for the degradation of organic pollutants in wastewater for the first time.The degradation performances of triphenyltin chloride(TPTCl),dimethyl phthalate(DMP),as well as rhodamine B(RhB) were investigated.The results indicated that removal efficiency of 50 mg/L RhB,60 mg/L DMP and 120 mg/L TPTCl can reach 88.6%, 92.5%and 89.4%for 60 min,50 min and 75 min,respectively.By comparison of removal efficiency,we found 206 nm is superior to 253.7 nm UV in wastewat...     

Silica-metalloporphyrins hybrid materials: preparation and catalysis to hydroxylate cyclohexane with molecular oxygen

Three types of novel silica-metalloporphyrins hybrid materials, Si-S-APTCPPFe, Si-S-APTCPPMn and Si-S-APTCPPCo, were prepared at room temperature by sol–gel method involving a thiol-ene polymerization reaction of 5-(4-allyloxy)phenyl-10,15,20-tri(4-chlorophenyl)porphyrin (APTCPP) with 3-mercaptopropyltrimethoxysilane (MPS). The hybrid materials were characterized by XRD, SEM, FT–IR, UV–Vis and TG, and were investigated as catalysts for the aerobic oxidation of cyclohexane. It is found that these hybrid materials are more efficient catalysts than the analogous non-supported metalloporphyrins for cyclohexane hydroxylation in metalloporphyrin–O₂–ascrobate system and the metal ion in the porphyrins significantly affected the catalytic efficiencies of these hybrid materials.     

Kinetics of reductive stripping of Pu(IV) in the tributylphosphate-kerosene/nitric acid-water system using dihydroxyurea

The kinetics of the reductive stripping of plutonium(IV) by dihydroxyurea (DHU) in 30% TBP/kerosene-HNO₃ system was studied with a constant interfacial area cell. The stripping rate of plutonium(IV) increases with the increase of the stirring speed of two phases and the interfacial area. The activation energy of this process is 28.4 kJ/mol. Under the given experimental conditions, the mass transfer of Pu is not controlled by redox reaction, but controlled by molecular diffusion from the organic phase to organic film layer and from the aqueous film layer to aqueous phase. The rate equation of reductive stripping (process is controlled by diffusion) was obtained as: r ₀ = k′[Pu(IV)]₀[DHU]_a ^0.16[HNO₃]_a ^−0.34. The rate constant k′ is (5.0±0.4)·10⁻² (mol/L)^0.18·min⁻¹ at 18.0°C.     

Synthesis,IR Spectrum,Thermal Analysis,and Crystal Structure of the Cyano‐bridged Heteronuclear Polymeric Complex: [Zn(teta)Ni(μ‐CN)2(CN)2]n

The heteronuclear polymeric complex, [Zn(teta)Ni(μ‐CN)₂(CN)₂]_n (teta: triethylenetetramine), was synthesized and characterized by elementel analysis, FT‐IR spectroscopy, thermal analysis and single crystal X–ray diffraction techniques. The complex crystallizes in the monoclinic system, space group P2₁/c and in which the Zn^II ion exhibits a distorted octahedral coordination by one tetradentate teta ligand and two bridging cyano groups as a trans position, whereas the Ni^II ion has square planer coordination and is coordinated by four cyano ligands. The decomposition reaction takes places in the temperature range 30–600 °C in the static air atmosphere.     

Syntheses,Spectra, Thermal Studies and Crystal Structures of Vitamin B13 Complexes of Nickel(II) with N,N,N′,N′‐Tetramethylethylenediamine and 2,2‐Dimethylpropane‐1,3‐diamine

Two nickel(II) complexes of vitamin B13 (H₃Or) with N,N,N′,N′‐tetramethylethylenediamine (tmen) and 2,2‐dimethylpropane‐1,3‐diamine (dmpen) were synthesized and characterized by means of elemental and thermal analyses, magnetic susceptibility, and IR and UV/Vis spectroscopic studies. The crystal structures of mer‐[Ni(HOr)(H₂O)₂(tmen)] · H₂O ( 1 ) and [Ni(HOr)(dmpen)₂] ( 2 ) were determined by using single‐crystal X‐ray diffraction. In the complexes, which crystallize in the triclinic system (space group for 1 ) and the monoclinic system (space group P2₁/c for 2 ), the Ni^II ions exhibit a distorted octahedral coordination. Ni^II ions are chelated by the deprotonated nitrogen atom of the pyrimidine ring and the oxygen atom of the carboxylate group, the distorted octahedral coordination completed by one tmen and two aqua ligands for 1 or two dmpen ligands for 2 .     

Correlation between hydrogen‐bonding interaction and mechanical properties of polyimide fibers

Novel co‐polymerization polyimide (PI) fibers based on 4,4′‐oxydianiline (ODA)‐pyromellitic dianhydride (PMDA) were prepared. 2‐(4‐Aminophenyl)‐5‐aminobenzimidazole (PABZ) containing the N? H group was introduced into the structure of the fibers as the proton donor. The results of Fourier transform infrared (FTIR) and dynamic mechanical analysis (DMA) showed that hydrogen bonding occured between the N? H group and chains, which strongly enhanced interchain interaction. This hydrogen bonding interaction increased the tensile strength and initial modulus of the PI fibers up to 2.5 times and 26 times, respectively, compared to those of homo‐PI PMDA‐ODA fibers with no hydrogen‐bonding interaction because of the absence of proton donors after the imidization process. In the mean time, glass transition temperature (T_g) of the modified PI fibers was found to be 410–440°C, which was higher than that of the homo‐PI PMDA‐ODA fibers. From the result, a novel access to molecular design and manufacture of high performance PI fibers with good properties could be provided. Copyright © 2009 John Wiley & Sons, Ltd.     

Asymmetrical Fluorene[2,3‐b]benzo[d]thiophene Derivatives: Synthesis,Solid‐State Structures,and Application in Solution‐Processable Organic Light‐Emitting Diodes

A series of novel asymmetrical fused compounds containing the backbone of fluorene[2,3‐b]benzo[d]thiophene (FBT) were effectively synthesized and fully characterized. Single‐crystal X‐ray studies demonstrated that the length of the substituent side chains greatly affects the solid‐state packing of the obtained fused compounds. DFT, photophysical, and electrochemical studies all showed that the FBTs have large band gaps, low‐lying HOMO energy levels, and therefore good stability toward oxidation. Moreover, the substituents strongly influence the fluorescence properties of the resulting FBT derivatives. The di‐n‐hexyl compound exhibits intense fluorescence in solution with the highest quantum yield of up to 91 %. Solution‐processed green phosphorescent organic light‐emitting diodes with the di‐n‐butyl derivative as the host material exhibited a maximum brightness of 14 185 cd m^?2 and a luminescence efficiency of 12 cd A^?1.     

Synthesis of a Photoresponsive Liquid‐Crystalline Polymer Containing Azobenzene

The synthesis of an oriented liquid‐crystalline photoresponsive polymer, prepared by polymerization of mono‐ and di‐acrylates, both of which contain azobenzene chromophores, is reported. The prepared free‐standing polymer film shows strong reversible photoinduced deformation upon exposure to unpolarized UV light at 366 nm, as a result of an optically induced isomeric change of the azobenzene moieties in the polymer network. The synthesis process is relatively simple and more efficient compared to conventional ones, and can be used to synthesize other liquid‐crystalline photoresponsive polymers. The use of this photoresponsive polymer film as an optical high‐pass/low‐pass switch under UV or natural light irradiation for a laser beam is demonstrated. This photoresponsive polymer may have applications in robotic systems, artificial muscles, and actuators in microelectromechanical systems (MEMS) and labs on chips.

     

甲醇制烯烃反应机理

本文综述了甲醇制烯烃（MTO）反应机理的研究进展,介绍了MTO反应的5个阶段：二甲醚平衡物的生成,反应诱导期,反应稳定期,二次反应和积碳失活,以及各个阶段存在的反应类型。总结了主要的机理模型及相应的实验论据,讨论了机理模型在各个反应阶段的应用,重点讨论了直接形成机理和hydrocabon pool机理。基于实验论据的支持,认为hydrocabon pool机理能更好地解释MTO反应。同时,对机理研究中采用的理论和试验方法进行了综述。