IN SITU OBSERVATION OF MELTING AND CRYSTALLIZATION BEHAVIORS OF POLY(ε-CAPROLACTONE) ULTRA-THIN FILMS BY AFM TECHNIQUE

The melting and crystallization behaviors of poly(ε-caprolactone) (PCL) ultra-thin films with thickness from 15 nm to 8 nm were studied by AFM technique equipped with a hot-stage in real-time. It was found that melting can erase the spherulitic structure for polymer film with high thickness. However, annealing above the melting point can not completely erase the tree-like structure for the thinner polymer film. Generally, the structure formation of thin polymer films of PCL is controlled not only by melting and crystallization but also by dewetting during thermal annealing procedures, and dewetting predominates in the structure formation of ultra-thin films. However, the presence of tree-like morphology at 75 °C may be due to the strong interaction between PCL and mica surface, which may stick the PCL chains onto the mica surface during thermal annealing process. Moreover, the growth of the dendrites was investigated and it was found that crystallization is followed from a dewetted sample, and the branches did not grow with the stems. The crystallization of polymer in the ultra-thin films is a diffusion-controlled process. Both melting and crystallization behaviors of PCL in thin films are influenced by film thickness.     

Halonickel 2,4-di-t-butyl-6-(quinolin-8-yliminomethyl)phenolates: Synthesis, characterization and ethylene reactivity

A series of nickel halides bearing 2,4-di-t-butyl-6-(quinolin-8-yliminomethyl) phenolate ligands was synthesized and characterized by IR spectroscopy and elemental analysis.Molecular structures of C1(R = H,X = Br) and C2(R = H,X = Cl) were further confirmed by single-crystal X-ray crystallographic studies,and revealed a distorted square planar geometry at nickel.Upon activation with diethylaluminum chloride(Et 2 AlCl),all nickel pre-catalysts displayed good catalytic activity [up to 9.3 × 10 5 g mol 1(Ni) h 1 ] for ethylene oligomerization with major dimerization.In the presence of methylaluminoxane(MAO),the nickel complex C1 was capable of ethylene polymerization under 3 MPa,and produced polyethylene products with narrow polydispersity(1.16 1.73) and molecular weights in the range of 2.6 4.95 kg/mol.     

Capability of DNA-fueled molecular machine in tuning association rate of DNA-functionalized gold nanoparticles

The capability of our newly developed DNA-machine-driven strategy in tuning the association rate of DNA-AuNPs was compared with that of linker-addition strategy which has potential practical applications in different fields. The new established strategy shows its superiority to the linker-addition strategy in tuning the association rate of DNA-AuNPs in both pre-incubation treatment and non-incubation treatment conditions since its two components (a complex and a catalyst-oligonucleotide) can be individually optimized to make the machine run at an optimal rate. This strategy will provide a more convenient and flexible option in designing an oligonucleotide detection system and building a complex and versatile device.     

An electrochemically prepared sky-blue light emitting ether functionalized polyfluorene as chemosensor for metal ions

Synthesis and electrochemical polymerization of 9,9-bis(2-(2-(2-methoxy ethoxy)ethoxy)ethyl)-fluorene(EO-F)into poly[9,9-bis(2-(2-(2-methoxy ethoxy)ethoxy)ethyl)-fluorene](EO-PF) films are reported. The boron trifluoride diethyl etherate electrolyte enables facile preparation of EO-PF films at lower potential compared to LiClO4/MeCN and the electrochemical polymerizations are discussed. The EO-PF shows good electrochemical behavior and can be dissolved in solvents such as DMSO and THF. The solubility of EO-PF in THF is 2 mg mL 1and the number average molecular weight is35300 with a polydispersity index of 1.65. The side chains on C9position of the monomer maintain unchanged after electrooxidation into corresponding polymer. The EO-PF dissolved in THF under 365 nm ultraviolet light is sky blue light emitting with the Commission Internationale de L Eclairage-CIE coordinates of(0.19, 0.15). The electropolymerized EO-PF is used for the first time in chemosensing metal ions, demonstrating fluorescence quenching for Mn2+and Fe3+while fluorescence enhancement for Cr6+ions.     

Synthesis, properties and electropolymerization of starshaped oligothiophenes with hexakis(fluoren-2-yl)benzene as core

Star-shaped oligothiophenes with hexakis(fluoren-2-yl)benzene (HFB) as cores were designed and synthesized. Grafting thiophene units to HFB results in a bond flattening of the core, and makes the molecules a flipping-twist shape. Their thermal, photophysical and electrochemical properties were studied. Highly cross-linked conjugated polymers can be produced by electropolymerization of T1-T3.     

Influence of clay on the morphology and phase separation behavior of poly(methyl methacrylate)/poly(styrene-co-acrylonitrile) blends

The effect of clay on the morphology and phase-separation behavior of poly(methyl methacrylate)/poly(styreneco-acrylonitrile)(PMMA/SAN) blends and the variation of clay dispersion have been investigated. With the evolution of phase separation in PMMA/SAN, most of the clays are first located at the boundaries between PMMA and SAN, and then gradually move to the PMMA-rich domain, owing to the affinity of clay to PMMA. The introduction of clay causes the increase of binodal and spinodal temperatures of PMMA/SAN and enlarges their metastable region, indicating the phase stabilizing effect of clay on the matrix. But the influence of clay on the cloud points obviously depends on the composition of PMMA/SAN. The selective adsorption of PMMA on the clay results in the difference between the composition of surface layer and that of polymer matrix. Hence, the clay plays the role of an agent changing the conditions of phase structure formation.     

Crystal orientation and melting behavior of poly(ɛ-Caprolactone) under one-dimensionally “hard” confined microenvironment

Crystal orientation and melting behavior of poly(ε-caprolactone) in a diblock copolymer of poly(ε-caprolactone)-block-poly(2,5-bis[4-methoxyphenyl]oxycarbonyl)styrene) (PCL-b-PMPCS) was investigated. The degrees of polymerization of the PCL and PMPCS block are 200 and 98, respectively. With the PMPCS in a columnar liquid crystalline phase, the diblock is rod-coil one, which exhibits a lamellar phase morphology with the PCL layer thickness of 15.2 nm. Since the glass transition temperature of PMPCS block is much higher than the melting temperature of PCL, the crystallization of PCL is in a one-dimensionally "hard" confinement environment. Mainly on the basis of two-dimensional wide-angle X-ray diffraction experiments, we identified the orientation of PCL isothermally crystallized at various crystallization temperatures (Tcs). At high Tcs (Tc≥10℃), the c-axis of the PCL crystal is along the layer normal of the microphase-separated sturcture. Decreasing Tc can result in the tilting of PCL c-axis with respect to the layer normal. The lower the Tc is, the more the c-axis inclines. Meanwhile, the b-axis of PCL remains perpendicular to the layer normal. At a very low Tc of -78℃, the orientation of the PCL crystals is completely random. For the samples isothermally crystallized at Tc≤10℃, double melting behavior can be observed. While the low temperature endotherm reflects the melting of the crystals originally formed at the Tc applied, the high temperature one is associated with the crystals subjected to the process of recrystallization/reorganization upon heating due to the annealing effect.     

Preparation of single-hole hollow polymer nanospheres by raspberry-like template method

Single-hole hollow polymer nanospheres were fabricated by raspberry-like template method using "graft-from" strategy through atom transfer radical polymerization (ATRP). Nanometer-sized silica spheres were covalently attached onto the surfaces of micrometer-sized silica spheres. Crosslinked polymer shells on the nano-sized spheres outside the attached area were formed by "graft-from" strategy through ATRP. After removal of the silica cores, single-hole hollow crosslinked polymer nanospheres were obtained. In this strategy, most of ATRP monomers may be used and thus many functional groups can be easily incorporated into the single-hole hollow crosslinked polymer nanospheres.     

四川S.suis2强毒株溶血素样蛋白HLP序列信息分析及克隆表达产物活性检测

对四川猪链球菌2型(S.suis 2)强毒株05ZYH33溶血素样蛋白(hemolysin-like protein,HLP)编码基因hlp进行序列信息分析、分子克隆表达及溶血活性检测,深入探讨HLP的致病机制.用Blast和Clustal X程序对HLP进行基因同源性分析,用Signal P 4.1和TMHMM Server 2.0分析HLP氨基酸序列.设计合成hlp引物进行PCR扩增,先后将hlp克隆入p MD-18T载体和p ET30a表达载体中,构建p ET30a::hly原核表达质粒.将重组质粒转化至E.coli BL21中诱导表达,并对重组HLP蛋白进行纯化和溶血活性检测.同源性分析表明HLP与多种具有溶血活性的蛋白相似性较高.氨基酸序列分析发现HLP具有信号肽和跨膜区,且由DUF21、CBS和Cor CHly C 3部分组成.序列测定显示hly片段全长1 335 bp,编码445个氨基酸.重组质粒经诱导表达和纯化后电泳显示,HLP分子量约为70 k Da,具有溶血活性.结果表明,HLP是一个膜结合蛋白,不同于能够分泌到细胞外的溶血素Suilysin.重组HLP具有一定的溶血效价,此可能与致病相关.     

弱拟正规子群对有限群的幂零性的影响

G的一个子群H称为在G中弱拟正规,如果对G的任意子群K,至少存在一个K的共轭子群Kx,x∈G,使得HKx=KxH.利用弱拟正规子群的概念,本文得到了关于有限群的幂零性的一些新刻画,给出了幂零群的一些充要条件.