Synthesis of grafted poly(p‐phenyleneethynylene) with energy donor–acceptor architecture via atom transfer radical polymerization: Towards nonaggregating and hole‐facilitating light‐emitting material

In this contribution, we demonstrate a new effective methodology for constructing highly efficient and durable poly(p‐phenyleneethynylene) (PPE) containing emissive material with nonaggregating and hole‐facilitating properties through the introduction of hole‐transporting blocks into the PPE system as the grafting coils as well as building the energy donor–acceptor architecture between the grafting coils and the PPE backbone. Poly(2‐(carbazol‐9‐yl)ethyl methacrylate) (PCzEMA), herein, is chosen as the hole‐transporting blocks, and incorporated into the PPE system as the grafting coils via atom transfer radical polymerization. The chemical structure of the resultant copolymer, PPE‐g‐PCzEMA, was characterized by NMR and gel permeation chromatography, showing that the desirable copolymer was obtained with the narrow polydispersity. The increased thermal stability of PPE‐g‐PCzEMA was confirmed by thermogravimetric analysis and differential scanning calorimetry along with its macroinitiator. The optoelectronic properties of this copolymer were studied in detail by ultraviolet‐visible absorption, photoluminescence emission and excitation spectra, and cyclic voltammogram (CV). The results indicate that PPE‐g‐PCzEMA exhibits the solid‐state luminescent property dominated by individual lumophores, and also the energy transfer process from the PCzEMA blocks to the PPE backbone with a relatively higher energy transfer efficiency in the solid‐state compared to that of the solution state. Additionally, the hole‐injection property is greatly facilitated due to the presence of PCzEMA, as confirmed by CV profiles. All these data indicate that PPE‐g‐PCzEMA is a good candidate for use in optoelectronic devices. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3776–3787, 2007     

质子滴线区新的缓发质子先驱核121Ce

藉助核反应⁹²Mo(³²S ,3n)产生了未知的缓发质子先驱核¹²¹Ce ,并利用氦喷嘴快速带传输系统和“p-γ”符合方法对它进行了鉴别 .测定了¹²¹Ce的半衰期 ( 1.1±0 .1 )s,观测了它的β缓发质子能谱 ,粗略地估计了它的β缓发质子衰变道的分支比约为1% .首次观测了先驱核¹¹⁹Ba,¹²¹Ba和¹²²La经过β缓发衰变在“子核”中产生的低位能级到基态的γ 跃迁.     

First Total Synthesis of 12-Hydroxy-13-methylpodocarpa-9, 11, 13-trien-3-one

12-Hydroxy-13-methylpodocarpa-9, 11, 13-trien-3-one 9 was isolated from the twigs ofCroton salutaris1. Many diterpenes exhibit significant bioactivities, such as antibac-terial and antitumour and 9 has a rare structure. In order to study the relationshipb…     

Crosslinked epoxy materials exhibiting thermal remendablility and removability from multifunctional maleimide and furan compounds

Crosslinked polymeric materials, which exhibit thermal remendability and removability through Diels–Alder (DA) and retro‐DA reactions, were obtained from using multifunctional maleimide and furan compounds as monomers. The synthesized monomers possess low melting points and good solubility in organo solvents to show excellent processing properties. The performance of DA and retro‐DA reactions were demonstrated with DSC and FTIR measurements. High performance of thermal remendablility and removability of the crosslinked materials were observed with SEM and solvent tests. These materials were applicable in advanced encapsulants and structural materials. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 905–913, 2006     

Divinylsiloxane‐bisbenzocyclobutene‐based polymer modified with polystyrene–polybutadiene–polystyrene triblock copolymers

Divinylsiloxane‐bisbenzocyclobutene (DVS‐bisBCB) polymer has very low dielectric constant and dissipation factor, good thermal stability, and high chemical resistance. The fracture toughness of the thermoset polymer is moderate due to its high crosslink density. A thermoplastic elastomer, polystyrene–polybutadiene–polystyrene triblock copolymer, was incorporated into the matrix to enhance its toughness. The cured thermoset matrix showed different morphology when the elastomer was added to the B‐staged prepolymer or when the elastomer was B‐staged with the DVS‐bisBCB monomer. Small and uniformly distributed elastomer domains were detected by transmission electron micrographs (TEM) in the former case, but TEM did not detect a separate domain in the latter case. A high percentage of the polystyrene–polybutadiene–polystyrene triblock copolymer could be incorporated into the DVS‐bisBCB thermoset matrix by B‐staging the triblock copolymer with the BCB monomer. The elastomer increased the fracture toughness of DVS‐bisBCB polymer as indicated by enhanced elongation at break and increased K1c values obtained by the modified edge‐lift‐off test. Elastomer modified DVS‐bisBCB maintained excellent electrical properties, high T_g and good thermal stability, but showed higher coefficient of linear thermal expansion values. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1591–1599, 2006     

Photocrosslinked poly(vinylbenzophenone)‐core micelles via mild Friedel–Crafts benzoylation of polystyrene amphiphiles

Photocrosslinkable poly(vinylbenzophenone)‐containing polymers were synthesized via a one‐step, Friedel–Crafts benzoylation of polystyrene‐containing starting materials [including polystyrene, polystyrene‐block‐poly(tert‐butyl acrylate), polystyrene‐block‐poly(ethylene oxide), polystyrene‐block‐poly(methyl methacrylate), and polystyrene‐block‐poly(n‐butyl acrylate)] with benzoyl trifluoromethanesulfonate as a benzoylation reagent. The use of this mild reagent (which required no added Lewis acid) permitted polymers with well‐defined compositions and narrow molecular weight distributions to be synthesized. Micelles formed from one of these benzoylated polymers, [polystyrene_0.25‐co‐poly(vinylbenzophenone)_0.75]₁₁₅‐block‐poly(acrylic acid)₁₄, were then fixed by the irradiation of the micelle cores with UV light. As the irradiation time was increased, the pendent benzophenone groups crosslinked with other chains in the glassy micelle cores. Dynamic light scattering, spectrofluorimetry, and Fourier transform infrared spectroscopy were all used to verify the progress of the crosslinking reaction. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2604–2614, 2006     

Probing the use of small‐angle light scattering for characterizing structure of titanium dioxide/low‐density polyethylene nanocomposites

Small‐angle light scattering (SALS) measurements were used to study the structure of titanium dioxide (TiO₂)/low‐density polyethylene (LDPE) nanocomposites. The results showed that the scattering from LDPE crystalline structures and the scattering from TiO₂ nanoparticles can be resolved and separated. It is shown that the independent effects of crystallization conditions and the presence of nanoparticle aggregates on the spherulitic structure of the LDPE matrix can be determined by analyzing the scattering patterns using the methods proposed. From the SALS results, we conclude that the nanoparticle surface chemistry affects both nucleation of spherulites and their structure particularly under rapid cooling conditions. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1084–1095, 2006     

三种瓜环与4,4′-联吡啶及N,N′-二甲基4,4′-联吡啶盐酸盐相互作用的研究

以七元瓜环(Q[7])和新型椭圆型改性瓜环———对称四甲基取代六元瓜环(TM eQ[6])为主体,4,4′-联吡啶的盐酸盐(44)以及N,N′-二甲基4,4′-联吡啶的盐酸盐(dm44)为客体的主客体相互作用进行了考察.实验结果表明,Q[7]与客体44及dm44作用体系中,客体为了更有效地被主体Q[7]包结,在Q[7]内腔中呈倾斜状分布的几率最高.用核磁共振、循环伏安以及紫外吸收光谱对实验结果进行了印证和补充,验证了TM eQ[6]与客体44及dm44可发生较强的相互作用,形成一维的自组装超分子结构.核磁共振以及循环伏安方法的实验结果表明,没有观察到Q[6]与客体44及dm44的明显作用,而紫外吸收光谱方法证实,Q[6]与客体44确实存在一定的相互作用,比较主客体的结构特征,该作用体系也可能存在自组装的一维超分子结构等多种作用形式.     

广义分布参数系统的状态反馈稳定性问题(1)

关于系统的状态反馈稳定性问题的研究一直是现代控制理论研究的重要问题之一.广义分布参数系统是比分布参数系统更广的一类系统,在研究复合材料热导体中的温度分布等问题时会出现这样的系统.本文讨论了H ilbert空间中一阶广义分布参数系统的状态反馈稳定性问题.应用泛函分析及线性算子半群理论的方法给出了使闭环广义分布参数系统渐进稳定的充要条件,充分条件及状态反馈的构造性表达式.这对研究广义分布参数系统的状态反馈稳定性问题具有重要的理论价值.