Controlled/“Living “Radical Polymerization of(-)-Menthyl Methacrylate

The atom transfer radical polymerization(ARP)of (-)-menthyl methacrylatc((-)-MnMA) mediated by CuCl/bipyridine and ethy1 2-bromopropionate or 1-phenylethyl bromide in THF system has been studied.The dependence of the specific rotation on molecular weight and the CD of Poly((-)-MnMA) thus obatined was investigated.     

Dendritic Macroinitiator for the Ring—Opening Polymerization of γ—Benzyl L—Glutamate N—Carboxyanhydride

Much effort has been dedicated to the molecular design and synthesis of model proteins to define protein folding interactions and to develop protein-based materials. Among them, the ring-opening polymerization of -amino acid-N-carboxyanhy- drides (NCAs) has drawn much attention because the resulting artificial polypeptides have wide applications in biotechnology, biomineralization and diagnostics1, 2. It is well known that dendrimers are hyperbranched macromolecules possessing a very high co…     

Reaction Ergodography and Transition State Analyses of the Addition of AIH_3 to Acetylene

The present paper covers the reaction ergodography for the addition of AlH3 to acetylene investigated by ab initio calculation with RHF/3-21G basis set. The changes in some physical properties along the reaction path (IRC) are presented. The formations of FMOs of the transition state have been analyzed according to the Fukui' s method. On the basis of the perturbation theory and Wolfsborg Helmholtz formula, we calculated the FMO' s energy orders of TS and its formation that shows the HOMO of TS consists of LUMO, HOMO of AlH3 and HOMO of HCCH.     

热重质谱联用(TG/MS)系统的建立和应用

将两种商品型分析仪器热重（TG）和质谱（MS）联用，并将这一热重质谱联用系统（TG／MS）应用于含酚废水的催化氧化和煤燃烧的过程研究，在获取样品重量变化的同时对逸出气相产物进行了在线检测，获取了苯酚氧化反应的历程和煤燃烧过程中氮、硫氧化物的逸出信息。     

Preparation of porous polylactide microspheres by emulsion‐solvent evaporation based on solution induced phase separation

Porous polylactide (PLA) microspheres were fabricated by an emulsion‐solvent evaporation method based on solution induced phase separation. Scanning electron microscopy (SEM) observations confirmed the porous structure of the microspheres with good connectivity. The pore size was in the range of decade micrometers. Besides large cavities as similarly existed on non‐porous microspheres, small pores were found on surfaces of the porous microspheres. The apparent density of the porous microspheres was much smaller than that of non‐porous microspheres. Fabrication conditions such as stirring rate, good solvent/non‐solvent ratio, PLA concentration and dispersant (polyvinyl alcohol, PVA) concentration had an important influence on both the particle size and size distribution and the pore size within the microspheres. A larger pore size was achieved at a slower stirring rate, lower good solvent/non‐solvent ratio or lower PLA concentration due to longer coalescence time. Copyright © 2005 John Wiley & Sons, Ltd.     

聚苯基（聚苄基）甲基硅氧烷的氟烷基化反应研究

通过苯基甲基二乙氧基硅烷和苄基甲基二乙氧基硅烷的缩合反应制备了聚苯基甲基和聚苄基甲基硅氧烷。研究了它们与含氟酰基过氧化物间的反应。经酸碱滴定及ＩＲ、＾１Ｈ ＮＭＲ和＾１９Ｆ ＮＭＲ光谱分析确证反应主要生成苯环上氟烷基取代产物。通过测定经氟烷基化后聚硅氧烷处理的玻璃表面的接触角，初步评价了氟烷基化率对其表现性能变化的影响。     

Total synthesis of polycavernoside A, a lethal toxin of the red alga Polycavernosa tsudai

[structure: see text] Two approaches to the synthesis of the aglycon 120 of polycavernoside A (1) were developed, only one of which was completed. The successful "second-generation" route assembled the aglycon seco acids 102 and 106 via Nozaki-Hiyama-Kishi coupling of aldehyde 70, prepared from methyl (S)-3-hydroxy-2-methylpropionate (72) and (S)-pantolactone (73), with vinyl bromide 71. The latter was obtained from a sequence which commenced from the silyl ether 24 of 3-hydroxypropionaldehyde and entailed cyclization of (Z)-zeta-hydroxy-alpha,beta-unsaturated ester 82. Regioselective Yamaguchi lactonization of trihydroxycarboxylic acids 102 and 106 and subsequent functional-group adjustments led to macrolactone 120, to which the fucopyranosylxylopyranoside moiety was attached. Stille coupling of the glycosidated aglycon 128 with dienylstannane 129 furnished polycavernoside A in a synthesis for which the longest linear sequence was 25 steps. The overall yield to lactone 120 was 4.7%.     

Two noncentrosymmetric complexes: [W(CO)4(bipy)] and [W(CO)4(phen)](bipy = 2,2′-bipyridine, phen = 1,10-phenanthroline) obtained through solvothermal synthesis and their optical properties

Solvothermal treatments of W(CO)₆ with 2,2′-bipyridine and 1,10-phenanthroline give [W(CO)₄(bipy)] (1) and [W(CO)₄(phen)] (2), respectively, which both crystallize in noncentrosymmetric space groups, suggesting that they meet the requirement of second harmonic generation (SHG) investigations. The preliminary experiment indicates that they are SHG active, and approximately estimated to be that of urea.     

A synthesis of trisubstituted alkenes by a Ru-catalyzed addition

Catalyzed by ruthenium trisacetonitrile hexafluorophosphate 4, the Alder-ene type reaction of alkenes and internal alkynes provides an effective way to synthesize trisubstituted alkenes. Unlike most typical olefination protocols, this reaction is atom economical, and affords trisubstituted alkenes with defined olefin geometry. The regioselectivity can be explained invoking a steric argument based on the proposed mechanism. The first C-C bond formation generally involves sterically less hindered carbons of the alkenes and alkynes. Modest to very high regioselectivity can be achieved depending on the steric difference of the two substituents of alkynes.