Synthesis and optoelectronic properties of silole‐containing polyfluorenes with binary structures

2,5‐Bis(2‐bromofluorene‐7‐yl)silole was prepared by a modified one‐pot synthesis with a reverse addition procedure, from which novel silole‐containing polyfluorenes with binary random and alternating structures (silole contents between 4.5 and 25% and high M_w up to 509 kDa were successfully synthesized. The well‐defined repeating unit of the alternating copolymer comprises a terfluorene and a silole ring. Optoelectronic properties including UV absorption, electrochemistry, photoluminescence (PL), and electroluminescence (EL) of the copolymers were examined. The different excitation energy transfers from fluorene to silole of the copolymers in solution and in the solid state were compared. The films of the copolymers showed silole‐dominant green emissions with high absolute PL quantum yields up to 83%. EL devices of the copolymers with a configuration of ITO/PEDOT/copolymer/Ba/Al displayed exclusive silole emissions peaked at around 543 nm and the highest EL efficiency was achieved with the alternating copolymer. Using the alternating copolymer and poly(9,9‐dioctylfluorene) as the blend‐type emissive layer, a maximum external quantum efficiency of 1.99% (four times to that of the neat film) was realized, which was a high efficiency so far reported for silole‐containing polymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 756–767, 2007     

2‐Cyanoprop‐2‐yl dithiobenzoate mediated reversible addition–fragmentation chain transfer polymerization of acrylonitrile targeting a polymer with a higher molecular weight

The reversible addition–fragmentation chain transfer (RAFT) polymerization of acrylonitrile (AN) mediated by 2‐cyanoprop‐2‐yl dithiobenzoate was first applied to synthesize polyacrylonitrile (PAN) with a high molecular weight up to 32,800 and a polydispersity index as low as 1.29. The key to success was ascribed to the optimization of the experimental conditions to increase the fragmentation reaction efficiency of the intermediate radical. In accordance with the atom transfer radical polymerization of AN, ethylene carbonate was also a better solvent candidate for providing higher controlled/living RAFT polymerization behaviors than dimethylformamide and dimethyl sulfoxide. The various experimental parameters, including the temperature, the molar ratio of dithiobenzoate to the initiator, the molar ratio of the monomer to dithiobenzoate, the monomer concentration, and the addition of the comonomer, were varied to improve the control of the molecular weight and polydispersity index. The molecular weights of PANs were validated by gel permeation chromatography along with a universal calibration procedure and intrinsic viscosity measurements. ¹H NMR analysis confirmed the high chain‐end functionality of the resultant polymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1272–1281, 2007     

2,2’—二硫代双(4,6—二叔丁基苯酚)的晶体和分子结构

一种塑解剂经高压液体色谱分离制备出主要成份2,2′—二硫代双(4,6二叔丁基苯酚)。由质谱分析得到分子量为474化学式为C_(28)H_(2)O_2S_2、晶体呈现孪生。基体单晶属三斜晶系,空间群为(?)PI(NO.2),晶体结构用直接法解出,=0.07。研究结果表明该分子是二硫代酚类化合物。在EI场中,S—S键断裂是主要断裂过程。晶体中,分子的一个环上的羟基是无序分布的。羟基与最邻近的硫原子形成氢键。     

Kinetic behaviour of aluminum naphthenate/benzene system in process of gelation and degradation

The kinetic behaviour of aluminum naphthenate/benzene system in the process of gelation and degradation was systematically studied. The results obtained from the kinetic experiments indicated that the gelation stage was in accordance with a kinetic model of an auto-catalytic first-order reaction, and the degradation stage was a simple first-order reaction. The rate constants in these two stages at various temperaturs were measured. And the determined apparent activation energies for the gelation stage and for the degradation stage are 27.5±2.0 and 37.7±2.3 kJ/mol, respectively.     

On the persistence of elliptic lower-dimensional tori in Hamiltonian systems under the first Melnikov condition and Rüssmann’s non-degeneracy condition

In this paper we formulate a theorem on the persistence of elliptic lower-dimensional invariant tori for nearly integrable analytic Hamiltonian systems under the first Melnikov condition and Rüssmann’s non-degeneracy condition, and give the measure estimates of parameters for the non-resonance conditions under Rüssmann’s non-degeneracy condition, which is essential for the proof of our result.     

Solvothermal synthesis of TiO2: anatase nanocrystals and rutile nanofibres from TiCl4 in acetone

This work reports a new synthetic approach for single‐phase TiO₂ nanomaterials by solvothermal treatment of titanium tetrachloride in acetone at 80–110 °C. Small, uniform, and yet size‐tunable (5–10 nm) anatase titania nanocrystallites were obtained using a low concentration of TiCl₄ in acetone (i.e., at molar ratios of TiCl₄/acetone ≤ 1:15) in the temperature range of 80–110 °C, while rutile nanofibers were synthesized using a high concentration of TiCl₄ (e.g., TiCl₄/acetone = 1:10) at 110 °C. Copyright © 2007 John Wiley & Sons, Ltd.     

Stagnation flow on a cylinder with partial slip--an exact solution of the Navier-Stokes equations

The stagnation slip flow on an axially moving cylinder is studied.The Navier–Stokes and energy equations reduce to nonlinearordinary differential equations under a similarity transform.For large slip, the flow field decays exponentially into potentialflow. The heat transfer can be expressed as an incomplete gammafunction. In general, the heat transfer increases with slip,Prandtl number and Reynolds number.     

Studies on the method of total synthesis of koumine: I. 4-Substituted 1,2-dihydropyridine derivatives and their function as a conjugated diene in Diels-Alder reaction

A route to the total synthesis of koumine has been suggested. Five 4-substituted 1, 2-d hydropyridine derivatives, which are supposed to be a conjugated diene of Diels-Alder reaction to produce the isoquinuclidine ring of koumine, have been synthesized. Only two of them were found to be able to undergo the Diels-Alder reaction. The stereochemistry of the reaction product has also been examined.     

Anchoring Properties of Nematic Liquid Crystals Studied Using the Attenuated Total Reflection Method

By using the attenuated total reflection method associated with the excitation of surface plasmons, the tilt angle of the liquid crystal director and its gradient at the surface are measured in a planar nematic cell as a function of the applied voltage. The surface anchoring anisotropy δπ of the liquid crystal and the surface elastic constant k_s, are found to be δπ = 0.288 erg/cm and k_s, = 9·12 × 10^-11 erg, respectively, when the boundary condition suggested by Barbero et al is used. The theoretical and experimental values obtained with this boundary condition and that of Mada are discussed. The results show that the boundary condition proposed by Barbero et al is in better agreement with the experiment.