Convenient synthesis of glycosyl bromide from 1-O-acetyl sugars by photo-irradiative phase-vanishing reaction of molecular bromine

The synthesis of glycosyl bromides from 1-O-acetyl sugars using a photo-irradiative phase-vanishing method involving molecular bromine was achieved. A bottom phase of molecular bromine was overlaid first with perfluorohexanes (FC-72), followed by overlaying with ethyl acetate containing a 1-O-acetyl sugar. Upon irradiation, the bromine layer gradually disappeared, leaving two phases. Glycosyl bromide was obtained in good yield from the ethyl acetate phase.     

含环氧基团的聚合物微球固载2,2,6,6-四甲基哌啶氮氧自由基催化剂的制备及其催化分子氧氧化苯甲醇

以甲基丙烯酸缩水甘油酯(GMA)为单体, 以乙二醇二甲基丙烯酸酯(EGDMA)为交联剂, 采用悬浮聚合法制得交联聚甲基丙烯酸缩水甘油酯(CPGMA)微球, 然后以4-羟基-2,2,6,6-四甲基哌啶氮氧自由基(4-OH-TEMPO)为试剂, 使CPGMA微球表面的环氧基团发生开环反应, 从而制得了TEMPO固载化微球TEMPO/CPGMA, 考察了制备条件对固载化反应的影响, 并采用多种方法对微球TEMPO/CPGMA进行了表征. 将微球TEMPO/CPGMA与CuCl组成共催化体系, 用于分子氧氧化苯甲醇, 考察了反应条件对催化体系性能的影响. 结果表明, 以含环氧基团的聚合物微球CPGMA为载体, 通过开环反应, 可成功地实现TEMPO的固载化, 开环反应属S_N2亲核取代反应, 适宜采用溶剂N,N''-二甲基甲酰胺和反应温度85℃. 非均相催化剂TEMPO/CPGMA与助催化剂CuCl构成共催化体系, 在室温、常压O₂条件下可高效地将苯甲醇氧化为苯甲醛, 产物选择性和产率分别为100%和90%. 主催化剂TEMPO与助催化剂CuCl适宜的摩尔比为1:1.2; 主催化剂适宜用量为0.90 g. 此外, TEMPO/CPGMA固体催化剂具有良好的循环使用性能.     

Synthesis of unnatural 3′-phospha-2′-deoxyfuranose nucleoside analogues

This Letter describes the synthesis of racemic analogues of unnatural 2′-deoxy nucleoside with a phosphorus atom replacing the carbon atom in the 3′-position. A seven-step sequence was developed in racemic series to afford unnatural 3′-phospha-2′-deoxyfuranose nucleosides. The phospha nucleoside analogues were tested against HCV, but did not show any antiviral activity at a 10 μM maximum concentration used for the inhibition assays of analogues 2-T, 2-C and 4-Tα.     

A triphenylamine based multi-analyte chemosensor for Hg and Cu ions in MeCN/H2O

A novel triphenylamine based oxidative chemosensor TOC was synthesized. The chromogenic and fluorogenic behaviors of TOC towards Hg²⁺ and Cu²⁺ ions in a binary mixture of MeCN/H₂O (9/1) were dramatically different. TOC displays colorimetric ‘naked eye’ recognition of Hg²⁺ and fluorogenic ‘turn on’ response towards Cu²⁺ via a unique cyclization reaction using two different detection modes. Moreover, TOCAZOL obtained from the oxidative cyclization reaction of TOC with Cu(ClO₄)₂ can be used as a selective fluorescent sensor toward Hg²⁺ ion.     

Synthesis of N-labeled 4-oxo-2,2,6,6-tetraethylpiperidine nitroxide for EPR brain imaging

A scalable synthetic route for ¹⁵N-labeled 4-oxo-2,2,6,6-tetraethylpiperidine nitroxide (¹⁵N-TEEPONE) is described. This ¹⁵N-labeled nitroxide is suitable for electron paramagnetic resonance imaging of brain, and its higher sensitivity compared with that of its ¹⁴N-counterpart is an important advantage of the labeled derivative.     

TEMPO/固载化席夫碱铜配合物共催化剂在分子氧氧化苯甲醇过程中的催化性能

通过大分子反应,将苯甲醛(BA)和邻氨基苯酚(AP)形成的双齿席夫碱配基键合在交联聚甲基丙烯酸缩水甘油酯(CPGMA)微球表面,形成固载有席夫碱配基的载体微球BAAP-CPGMA,再通过与铜盐的配位螯合反应,制备了固载有席夫碱铜配合物的微球[Cu(BAAP)2]-CPGMA.将该固载化铜配合物与均相的2,2,6,6-四甲基哌啶氮氧自由基(TEMPO)构成共催化体系TEMPO/[Cu(BAAP)2]-CPGMA,应用于分子氧氧化苯甲醇的催化氧化过程.我们考察了该共催化体系的催化性能,并探索研究了催化氧化机理.实验结果表明,共催化体系TEMPO/[Cu(BAAP)2]-CPGMA可在温和条件下(室温、常压的氧气)高效地将苯甲醇氧化为苯甲醛(选择性100%,苯甲醛产率93%),并具有良好的循环使用性能.     

锰催化的C?C键生成反应研究进展

迄今为止,贵金属(铑、钯、钌等)在过渡金属催化的碳碳键生成反应中发挥着主导作用,然而使用廉价金属催化剂更符合可持续发展的要求。锰是地壳中含量排第三位的过渡金属,价格便宜,环境危害性小,有潜力成为贵金属催化剂的替代品并发挥其自身独特的反应性。尽管锰参与的当量反应有大量文献报道,目前锰催化的反应尤其是碳碳键生成反应的发展还不成熟,如何实现高效的催化循环是锰催化领域面临的主要难题之一。本文对锰催化的付-克烷基化反应、格氏试剂的酰化反应、偶联反应、碳金属化反应、自由基反应和碳氢键活化反应进行了综述。     

Effects of incorporation of modified silica nanoparticles on the mechanical and thermal properties of PMMA

Silica nanoparticles of various sizes have been incorporated by melt compounding in a poly(methyl methacrylate) (PMMA) matrix to enhance its thermal and mechanical properties. In order to improve nanoparticles dispersion, PMMA grafted particles have been prepared by atom transfer radical polymerization (ATRP) from well-defined silica nanoparticles. This strategy was expected to ensure compatibility between both components of the PMMA nanocomposites. TEM analysis have been performed to evaluate the nanosilica dispersion whereas modified and non-modified silica/PMMA nanocomposites thermal stability and mechanical properties have been investigated by both thermogravimetric and dynamical mechanical analysis.     

过氧亚硝酸与酪氨酸的反应机理

用密度泛函理论(DFT)研究了过氧亚硝酸与酪氨酸的反应机理. 在B3LYP/6-311G(d,p)水平上对该反应体系的反应物、中间体、过渡态和产物进行了几何构型优化并计算了振动频率和能量. 计算结果表明, 过氧亚硝酸不易直接与酪氨酸反应, 而是先分解产生自由基(·OH和·NO2), 而后再与酪氨酸分步作用. 过氧亚硝酸与酪氨酸的反应生成两种主要产物, 分别为3-羟基酪氨酸和3-硝基酪氨酸, 这一结论与实验所得到的结果一致. 此外在同一计算水平上采用SCRF(PCM)方法计算了溶剂化效应, 结果表明, 极性溶剂可以增加自由基结合的稳定化能, 并降低反应通道的活化能, 有利于反应的进行.     

利用电子自旋共振技术捕捉烯类单体双光子聚合反应的自由基信号

<正>自1999年烯类单体的双光子聚合方法被发现以来[1],其产物在光开关制备[2]、光子晶体[3]、微机械[4]及三维微加工[5]等领域得到了广泛的应用.由此,烯类双光子聚合机理也成为人们研究的焦点[6].到目前为止,研究者们普遍认为烯类单体的双光子聚合反应属于自由基历程,各种利用双光子