Synthesis of optically active poly(N‐propargylsulfamides) with helical conformation

A novel chiral N‐propargylsulfamide monomer ( 1a ) and its enantiomer ( 1b ) were synthesized and polymerized with (nbd)Rh⁺B^?(C₆H₅)₄ as a catalyst providing poly(1) (poly( 1a ) and poly( 1b )) in high yields (≥99%). Poly(1) could take stable helices in less polar solvents (chloroform and THF), demonstrated by strong circular dichroism signals and UV–vis absorption peaks at about 415 nm and the large specific rotations; but in more polar solvents including DMF and DMSO, poly(1) failed to form helix. Quantitative evaluation with anisotropy factor showed that the helical screw sense had a relatively high thermal stability. These results together with the IR spectra measured in solvents showed that hydrogen bonding between the neighboring sulfamide groups is one of the main driving forces for poly(1) to adopt stable helices. In addition, copolymerization of monomer 1a and monomer 2 was conducted, the solubility of poly(1) was improved drastically. However, the copolymerization had adverse effects on the formation of stable helices in the copolymers. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 500–508, 2007     

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     

化学位移各向导性对半整数自旋四极核的2D NMR章动的影响

考察了化学位移各向异性对半整数自旋四极核2D NMR章动的影响.用数值方法对2D NMR章动实验的演化期的Hamiltonian矩阵进行对角化,然后用帐篷法进行粉末平均,获得了自旋为I=3/2、5/2、7/2和9/2的四极核在不同化学位移各向异性下的2D NMR章动谱.实验结果与理论计算符合较好.     

布拉格方程在高聚物结构研究中的应用

本文将布拉格方程推广应用到高聚物的结构研究中，得到了经不同剂量辐照的聚乙烯单晶的长周期，并辅以示差扫描量热法研究了γ－射线辐照对聚乙烯单晶结构的影响．     

Atom transfer radical polymerization directly from poly(vinylidene fluoride): Surface and antifouling properties

The direct preparation of grafting polymer brushes from commercial poly (vinylidene fluoride) (PVDF) films with surface‐initiated atom transfer radical polymerization (ATRP) is demonstrated. The direct initiation of the secondary fluorinated site of PVDF facilitated grafting of the hydrophilic monomers from the PVDF surface. Homopolymer brushes of 2‐(N,N‐dimethylamino)ethyl methacrylate (DMAEMA) and poly (ethylene glycol) monomethacrylate (PEGMA) were prepared by ATRP from the PVDF surface. The chemical composition and surface topography of the graft‐functionalized PVDF surfaces were characterized by X‐ray photoelectron spectroscopy, attenuated total reflectance/Fourier transform infrared spectroscopy, and atomic force microscopy. A kinetic study revealed a linear increase in the graft concentration of poly[2‐(N,N‐dimethylamino)ethyl methacrylate] (PDMAEMA) and poly[poly(ethylene glycol) monomethacrylate] (PPEGMA) with the reaction time, indicating that the chain growth from the surface was consistent with a controlled or living process. The living chain ends were used as macroinitiators for the synthesis of diblock copolymer brushes. The water contact angles on PVDF films were reduced by the surface grafting of DMAEMA and PEGMA. Protein adsorption experiments revealed a substantial antifouling property of PPEGMA‐grafted PVDF films and PDMAEMA‐grafted PVDF films in comparison with the pristine PVDF surface. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3434–3443, 2006     

Rebuilding of metal components with laser cladding forming

Laser cladding forming (LCF) is a novel powerful tool for the repairing of metal components. Rebuilding of V-grooves on medium carbon steel substrates has been carried out with laser cladding forming technique using stainless steel powder as the cladding material. Microstructure of the deposited layers has been characterized using optical microscopy (OM), scanning electron microscopy (SEM), energy dispersive X-ray microanalysis (EDAX), electron probe microanalysis (EPMA) and X-ray diffraction (XRD). Mechanical properties of the rebuilt V-groove samples have been evaluated by tensile and impacting tests and microhardness measurement. Experimental results show that good fusion bonding between the rebuilt layers and the substrate has been formed, and the microstructure of the cladding layers is mainly composed of fine, dense and defect-free epitaxial columnar dendrites. Due to the effect of grain size refinement, the tensile strength, impacting toughness, elongation and microhardness of the rebuilt samples have been greatly enhanced compared to those of the substrate. Microhardness is also very uniform throughout the rebuilt regions. With the growth of the deposited layers, the microhardness increases gradually. The good ductility of the deposited regions is verified by the SEM fracture analysis.     

Necessary and sufficient condition of the existence of global Hopf bifurcation for Hamiltonian systems

ForH C ² (,R) where 0 R ²ⁿ ,H (0)=0 and detH(0)0, the paper proves that there is a global Hopf bifurcation fromx=0 for Hamiltonian systemx=JH(x) iffJH(0)possesses purely imaginary eigenvalues. The work improves the corresponding result of J.C.Alexander and J. Yorke (Amer. J. Math., 100 (1978), 263–292).     

催化动力学电位法测定微量锰的研究

用结晶紫选择性电极（自制）以催化电位法对测定微量锰进行了研究。该方法测定标的线性范围为７～７４μｇ／Ｌ，对标准钢样中的锰含量测定结果满意，且操作方便。     

稀土铽配合物的有机发光二极管

有机小分子和有机高分子的发光二极管在可见光区内有非常高的量子效率，因而受到人们的高度重视．采用二胶（TPD），8羟基喹啉铝（Alq3）等有机小分子作为空穴和电子输运层所作的发光二极管[1]的量子效率可达10％，采用聚对苯乙炔（PPV）高分子聚合物作空穴输运层，有机小分子2