Synthesis and properties of new fluorene-containing copolymer via the catalytic dehydrocoupling reaction of 9,9-dipropargyl fluorene and 4,4′-diphenyl-2,6-dibromo-dithieno-[3,2-b:2′,3′-d]silole

ABSTRACT

New fluorene-containing copolymer was prepared via the catalytic dehydrocoupling reaction of 9,9-dipropargylfluorene and 4,4′-diphenyl-2,6-dibromo-dithieno-[3,2-b:2′,3′-d]silole in 44% yield. The resulting polymer was completely soluble in common organic solvents. The thermal behaviors and optical properties of the resulting polymer were measured and discussed. The chemical structure of polymer was characterized by NMR, IR, and UV-visible spectroscopies. The polymer showed characteristic wide UV-visible absorption band and blue PL maximum value at 440 nm, which is corresponding photon energy of 2.82 eV. The quantum yield (6.44%) of poly(DPF-DTS) was found to be 5 times higher than that of poly(DPF-bithiophene)).     

Tuning the Solid‐State Optical Properties of Tetracene Derivatives by Modification of the Alkyl Side‐Chains: Crystallochromy and the Highest Fluorescence Quantum Yield in Acenes Larger than Anthracene

In the solution state, there were no notable differences between the optical properties of a range of alkyl‐substituted tetracenes. However, in the solid state, their photophysical properties changed with respect to the length, shape, number, and substitution pattern of the alkyl side chains, as well as the distribution of two regioisomers. Remarkably, in the solid state, 1,4,7,10‐tetraisopropyltetracene exhibited the highest reported fluorescence quantum yield of any tetracene derivative (0.90). The changes in the optical characteristics of these tetracenes according to the arrangement of the tetracene rings and the color‐change mechanism in the solid state are discussed. Moreover, the world record in solid‐state fluorescence efficiency in acenes larger than anthracene is described. DOI 10.1002/tcr.201200003     

Effect of nematic ordering on the elasticity and yielding in disordered polymeric solids

The relation between elasticity and yielding is investigated in a model polymer solid by Molecular‐Dynamics simulations. By changing the bending stiffness of the chain and the bond length, semicrystalline and disordered glassy polymers — both with bond disorder — as well as nematic glassy polymers with bond ordering are obtained. It is found that in systems with bond disorder the ratio τ_Y/G between the shear yield strength τ_Y and the shear modulus G is close to the universal value of the atomic metallic glasses. The increase of the local nematic order in glasses leads to the increase of the shear modulus and the decrease of the shear yield strength, as observed in experiments on nematic thermosets. A tentative explanation of the subsequent reduction of the ratio τ_Y/G in terms of the distributions of the per‐monomer stress is offered. © 2017 Wiley Periodicals, Inc. J. Polym. Sci. Part B: Polym. Phys. 2017 , 55, 1760–1769     

Conditions of stability and instability for a pair of arbitrarily stratified compressible fluids in an arbitrary non-uniform gravity field

The work continues and develops authors’ previous investigation of stability in the small for a two-layer system of inhomogeneous compressible fluids in the uniform gravity field. Here we present a solution of a similar problem in the case of arbitrary non-uniform potential gravity field. The equilibrium stratification of both density and elastic properties of the fluids is supposed arbitrary, as well as the shape of open on top reservoir filled by the fluids. The problem of stability of equilibrium is analyzed as the corresponding problem for the non-linearly elastic bodies, basing on the static energy criterion with regard for the boundary conditions at all parts of the boundary. The crucial element of the analysis is conversion of the quadratic functional of second variation of total potential energy of the system into a “canonical” form that enables to determine its sign. Making use of this canonical form, we obtain almost coinciding with each other necessary and sufficient conditions for stability (those being valid also for an arbitrary number of layers).     

The synthesis and fluorescence properties of novel chromenone-crown ethers

o-Dihyroxy-3-phenylchromenone derivatives, namely, 6,7-dihydroxy-3-(3′,4′-dimethoxyphenyl)chromenone and 6,7-dimethoxy-3-(3′,4′-dihydroxyphenyl)chromenone, were obtained from 2,4,5-trihydroxybenzaldehyde/3,4-dimethoxyphenylacetic acid and 2-hydroxy-4,5-dimethoxybenzaldehyde/3,4-dihydroxyphenylacetic acid, respectively, in the presence of acetic anhydride and sodium acetate under an inert atmosphere, after treatment with MeOH/HCl(aq). The chromenone-crown ethers were prepared from cyclic condensation of o-dihydroxy-3-phenylchromenones with poly(ethylene glycol) ditosylates in the presence of CH₃CN/alkali metal carbonates. The chromatographically purified novel chromenone-crown ethers were identified by ¹H NMR, MALDI-TOF mass spectrometry and elemental analysis. The fluorescence and UV–vis spectroscopic properties of the obtained chromenone-crown ethers and their complexes with Li⁺, Na⁺ and K⁺ perchlorate salts were estimated in acetonitrile. The quantum yields of novel chromenone-crown ethers were determined by the comparative method.

     

氯化铜的少溶剂固态连串配位化学反应

在少量水的存在下,由于 NH₄[CuCl₃]对水不稳定,CuCl₂·2H₂O 与氯化铵的配位化学反应只能得到 1:2 产物(NH₄)₂[CuCl₄(H₂O)₂];但在无水乙醇中,无水 CuCl₂与氯化铵按 1:1或 1:2的物质的量之比混合时,能相应地得到 NH₄[CuCl₃]或(NH₄)₂[CuCl₄]。CuCl₂·2H₂O与 2,2''-联吡啶(bipy)的少溶剂固态化学反应仍能像固态化学反应一样,根据反应物的配比生成相应的唯一产物,但在物质的量之比为1:1的反应中发现1:2产物曾经形成。热力学分析说明,如果连串反应的后一步的Δ_rG^⊖大于前一步的,则上述反应现象是可能的。     

On the determination of the point of fracture initiation by the load separation criterion in J-testing of ductile polymers

The application of an experimental approach based on the load separation criterion for the determination of the point of fracture initiation in a fracture test on a ductile polymer was critically examined. To this aim, the fracture process outlined by the application of this method was related to that described by the visual analysis of the fracture surfaces obtained in fracture tests on nominally identical specimens, in which different levels of crack extension were produced. The material examined was an acrylonitrile-butadiene-styrene (ABS) resin, and the fracture tests were performed at low loading rate on single-edge notched in bending specimens.The results demonstrated that this load separation criterion based methodology is a promising approach for the determination of the point of fracture initiation, and for material fracture resistance, J_Ic, evaluation. The method also has experimental simplicity and a high degree of repeatability.     

Rheological Properties of Model and Crude Oil Systems when Wax Precipitate under Quiescent and Flowing Conditions

Wax precipitation and deposition is a recurring challenge in transportation of crude oil, and increased knowledge about the behavior of such systems is necessary. Microscopy and differential scanning calorimetry were used to follow the crystallisation of wax for two model systems. The amount of solid was also determined by the latter method as well. The flow and viscoelastic behavior were investigated around the wax precipitation temperature, and the yield stress was determined both after dynamic and static cooling. Interpretation of the results was carried out in view of crystal growth and microstructure of the wax crystals. The variables that were studied were wax composition, amount of wax and thermal and shear history.     

氢键准则在DMSO水溶液中应用的评价

利用分子动力学模拟方法, 分别采用几何准则和能量准则分析了不同浓度下的二甲基亚砜(DMSO)水溶液的氢键统计和动力学等特性. 结果显示, 两种氢键准则可以很好地反映出溶液的氢键性质随浓度的变化趋势. 通过分析比较发现, 由于几何准则不能有效地排除具有弱对势能的分子对, 因此其统计的氢键数量要大于能量准则的结果.此外, 能量准则对于分子间相对取向的区分存在不足, 进而引起氢键寿命的计算结果偏大.因此,为使氢键分析更加准确, 本文建议使用几何-能量混合型氢键准则.     

A blow‐up criterion to the 2D full compressible magnetohydrodynamic equations

We establish a new regularity criterion for the 2D full compressible magnetohydrodynamic system in a bounded domain. Copyright © 2014 John Wiley & Sons, Ltd.