Amphiphilic thermoset elastomers from metal‐free,click crosslinking of PEG‐grafted silicone surfactants

The hydrophobicity of silicone elastomers can compromise their utility in some biomaterials applications. Few effective processes exist to introduce hydrophilic groups onto a polysiloxane backbone and subsequently crosslink the material into elastomers. This problem can be overcome through the utilization of metal‐free click reactions between azidoalkylsilicones and alkynyl‐modified silicones and/or PEGs to both functionalize and crosslink silicone elastomers. Alkynyl‐functional PEG was clicked onto a fraction of the available azido groups of a functional polysiloxane, yielding azido reactive PDMS‐g‐PEG rake surfactants. The reactive polymers were then used to crosslink alkynyl‐terminated PDMS of different molecular weights. Using simple starting materials, this generic yet versatile method permits the preparation and characterization of a library of amphiphilic thermoset elastomers that vary in their composition, crosslink density, elasticity, hydrogel formation, and wettability. An appropriate balance of PEG length and crosslink density leads to a permanently highly wettable silicone elastomer that demonstrated very low levels of protein adsorption. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1082–1093     

Fused vs. spiro: Kinetic,not thermodynamic preference may direct the reaction of α-carbonyl oxonium ylides

Rh(II)-catalyzed decomposition of certain cyclic α-diazocarbonyl compounds in the presence of cyclic ethers has been shown to give bicyclic ring expansion products. These are thought to arise from a [1,4]-alkyl shift toward the carbonyl oxygen atom and are in contrast with the recently observed spirocyclic products of a Stevens-type [1,2]-alkyl shift within the postulated oxonium ylide intermediate. Quantum chemical calculations performed at the B3LYP/6-31G* level of theory showed that the former reaction pathway (toward fused bicycles) is kinetically preferred.     

Diastereoselective Alkylation of (Diene-Aldehyde)Fe(CO)3 Complexes with Functionalized Zinc-Copper Reagents NuCu(CN)Znl

Addition of functionalized zinc-copper reagents to the title complexes proceeds in a highly diastereoselective fashion to afford dienol complexes. The relative configurations of adducts 3d were determined by single X-ray diffraction analysis.     

超声光栅实验及其多普勒频移的一种简单研究方法

采用光子学方法,对超声光栅衍射实验和实验中出现的多普勒频移现象进行了研究,所得结论与采用光的波动性观点的惠更斯-菲涅耳原理及傅里叶变换等常规方法相同.该方法进一步加深了对衍射的本质和光的粒子性的理解并对光子的信息传递能力有初步的认识.     

天文斑点成像技术中的噪声影响分析

为进一步说明天文像复原新方法-迭代位移叠加法的性质，对探测器的附加噪声在斑点干涉术、斑点掩模法和迭代位移叠加法中的影响分别进行了分析。结果表明：在斑点掩模法中，复杂的噪声高阶矩统计被引入了重谱的噪声偏差，因此对噪声极为敏感，使数据处理更加复杂化；与斑点掩模法相比，迭代位移叠加法仅涉及对噪声的一阶矩统计平均，所以此新方法的特点是对噪声不敏感，具有图像复原处理过程简单快捷的优越性。     

飞秒孤子传输演化的数值研究

利用分步傅里叶法数值模拟了飞秒孤子在光纤中的传输演化过程。对光纤中单个孤子的传输及二阶孤子的自陡峭效应和自频移效应进行了分析,指出在一定的参数取值范围内,自频移效应对二阶fs孤子传输的影响要比自陡峭效应大,占主导地位,且对自陡峭效应有一定的抑制作用。     

光纤光栅激光器激射波长的研究

一般认为，用光纤光栅作选频元件的光纤激光器，激射波长与光纤光栅中心反射波长一致，本文报道了不同的实验研究结果。通过细致的实验研究，发现光纤光栅激光器激射波长相对于光纤光栅中心反射波长有一定的偏移。激射波长可以出现在光栅中心反射波长的长波端，也可以出现在其短波端。对不同腔结构的掺镱、掺铒光纤光栅激光器的深入研究证明，谐振腔的各向异性对激光器的激射波长偏移起到决定性的作用，波长最大偏移量主要受限于光纤光栅的反射带宽。通过激光腔内的偏振控制器改变谐振腔的各向异性，可以在光纤光栅的反射带宽内控制激射波长的位置。     

Polymerization behaviors of racemic and chiral amphiphilic monomers in organized bilayer membranes of lamellar liquid crystalline phase

A racemic amphiphilic monomer, n‐dodecyl glyceryl itaconate (DGI), forms bilayer membranes in water in the presence of small amount of ionic cosurfactant and shows iridescent color. A chiral DGI, S‐DGI, also shows an iridescent property, but with a rather red shift in the color, which can be ascribed to the increased packing density of the monomer in the bilayer membranes. Chrial DGI has a more compact packing density than racemic one owing to closer distance between the monomer molecules; the conversion rate, however, is slower than that of racemic one when H₂O₂ is used as an initiator. When the initiator is changed to an amphiphilic one, 4‐(2‐hydroxyethoxy) phenyl‐(2‐hydroxy‐2‐propyl) ketone (Irgacure 2959), the chiral DGI shows even a little faster conversion rate than that of racemic one. The NMR chemical shift results of protons in benzene ring show that the molecules of Irgacure 2959 insert into the bilayer membranes. The molecular weights of the corresponding polymers prove that the initiation by H₂O₂ is restricted compared to that by Irgacure 2959. It is concluded that the decelerated polymerization behavior of chiral DGI initiated by H₂O₂ is a result of limited diffusion of the initiator into the lamellar bilayer structures. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4891–4900, 2007