Combined lipase-catalyzed resolution/Mitsunobu esterification for the production of enantiomerically enriched arylalkyl carbinols

Several arylalkyl carbinols [1-indanol, 1-tetralol, 1-phenylethanol, 1-(1-naphthyl)ethanol, 1-(2-naphthyl)ethanol, 1-(4-methoxyphenyl)ethanol, 1-acenaphthenol] were deracemized through sequential combinations of lipase-catalyzed resolution and Mitsunobu inversion. The corresponding (R)-acetates were obtained in 72–83% yield and 89–99% ee.     

钒氧阴离子团簇与小分子碳氢化合物反应的实验和理论研究

为了在分子层次上揭示相关催化反应的机理, 人们对过渡金属氧化物团簇与碳氢化合物分子反应进行了大量研究. 相比于过渡金属氧化物团簇阳离子, 阴离子对一些碳氢化合物的活性弱得多, 因此研究还很少. 在本工作中, 我们通过激光溅射产生钒氧团簇阴离子VxOy, 产生的团簇在接近热碰撞条件下与烷烃(C2H6和C4H10)以及烯烃(C2H4和C3H6) 在一个快速流动反应管中进行反应, 飞行时间质谱用来检测反应前后的团簇分布. 在VxOy与烷烃的反应中, 生成了产物V2O6H-和V4O11H-; 在与烯烃的反应中, 产生了相应的吸附产物V4O11X-(X=C2H4或C3H6). 密度泛函理论计算表明: V2O-6和V4O-11可以活化烷烃(C2H6和C4H10)的C—H键, 也可以与烯烃(C2H4和C3H6)发生3+2环化加成反应形成一个五元环结构(-V-O-C-C-O-), C—H键活化与环加成反应都需经历可以克服的反应能垒. 理论计算与实验观测结果相符合. V2O-6和V4O-11团簇都具有氧原子自由基(O·或O-)的成键特征, 活性O-物种也经常出现在钒氧催化剂表面, 因而本研究在分子水平上, 揭示了表面活性氧物种与碳氢化合物反应的机理.     

白刺与枸杞中微量元素含量的对比研究

采用ICP-AES法对生长在同一区域内的白刺与枸杞根茎中的8种微量元素的含量进行了分析测定。结果表明,两种植物根茎中8种元素含量丰富,并且差异明显,为以后的开发利用提供了基础数据。     

钒氧阴离子团簇与小分子碳氢化合物反应的实验和理论研究

为了在分子层次上揭示相关催化反应的机理, 人们对过渡金属氧化物团簇与碳氢化合物分子反应进行了大量研究. 相比于过渡金属氧化物团簇阳离子, 阴离子对一些碳氢化合物的活性弱得多, 因此研究还很少. 在本工作中, 我们通过激光溅射产生钒氧团簇阴离子VxOy, 产生的团簇在接近热碰撞条件下与烷烃(C2H6和C4H10)以及烯烃(C2H4和C3H6) 在一个快速流动反应管中进行反应, 飞行时间质谱用来检测反应前后的团簇分布. 在VxOy与烷烃的反应中, 生成了产物V2O6H-和V4O11H-; 在与烯烃的反应中, 产生了相应的吸附产物V4O11X-(X=C2H4或C3H6). 密度泛函理论计算表明: V2O-6和V4O-11可以活化烷烃(C2H6和C4H10)的C—H键, 也可以与烯烃(C2H4和C3H6)发生3+2环化加成反应形成一个五元环结构(-V-O-C-C-O-), C—H键活化与环加成反应都需经历可以克服的反应能垒. 理论计算与实验观测结果相符合. V2O-6和V4O-11团簇都具有氧原子自由基(O·或O-)的成键特征, 活性O-物种也经常出现在钒氧催化剂表面, 因而本研究在分子水平上, 揭示了表面活性氧物种与碳氢化合物反应的机理.     

Synthesis, structure and photochromic properties of a novel 1,6-hexanediamine trimolybdate supramolecular compound

A novel supramolecular compound 1,6-hexanediamine trimolybdate ((C₆H₁₈N₂)[Mo₃O₁₀], denoted as HDAMo) has been synthesized by a hydrothermal method and its structure has been characterized by elemental analyses, Fourier transform infrared (FT-IR) spectra, single-crystal X-ray diffraction (XRD) technique. This single crystal compound consists of protonated 1,6-hexanediamine (HDA) cations and polyoxometalate [Mo₃O₁₀]²⁻ anions. Its crystal structure belongs to monoclinic system (space group P2₁/n) with a=7.7508(14), b=11.467(2), c=16.167(3) Å, β=92.689(3)°, V=1435.3(5) Å³, Z=4 and D_calc=2.619 g cm⁻³. The final statistics based on F² are GOF=0.980, R₁=0.0261 and wR₂=0.0506 for I>2σ(I). XRD analysis revealed that in the crystal structure of HDAMo, novel infinite [Mo₃O₁₀]²⁻ chains parallel to a axis are made up of distorted MoO₆ octahedra connected by corners and edges. The protonated HDA cations occupy channels formed by [Mo₃O₁₀]²⁻ chains and exhibit strong hydrogen bond interactions to terminal and bridging oxo groups of the chains. The [Mo₃O₁₀]²⁻ chains linked through protonated HAD cations formed a one-dimensional network. The HDAMo compound shows novel photochromic properties, i.e., its color changes from white to reddish brown gradually under UV irradiation. XRD, FT-IR, ESR spectra and XPS are used to investigate the photochromic behavior of the compound.     

Tunable pores in mesoporous silica films studied using a pulsed slow positron beam

Positron annihilation lifetime spectroscopy (PALS) based on a pulsed slow positron beam was applied to study mesoporous silica films, synthesized using amphiphilic PEO–PPO–PEO triblock copolymers as structure-directing agents. The pore size depends on the loading of different templates. Larger pores were formed in silica films templated by copolymers with higher molecular-weights. Using 2-dimensional PALS, open porosity of silica films was also found to be influenced by the molecular-weight as well as the ratio of hydrophobic PPO moiety of the templates.     

Conformation and size of humic substances: Effects of major cation concentration and type,pH, salinity,and residence time

The macromolecular structure of humic substances (HS), i.e. molecular size, shape, conformation, and weight is believed to control key physico-chemical reactions in aquatic systems. However, these properties of HS are still deeply a matter of debate. Furthermore, they are affected by solution physico-chemical parameters such as ionic strength, pH, and chemical composition, etc. To better understand aggregation processes of HS in natural waters, the effects of cation concentration and type, water composition, and pH on the size and conformation of the Suwannee River Humic Acid (SRHA) were investigated with synthetic solutions. The size and the conformation of the SRHA in NaCl and CaCl₂ solutions at different concentrations (0.001–0.5 M) and pH (4.5–9.3) were determined using the photon correlation spectroscopy (PCS) and transmission electron microscopy (TEM), respectively. In addition, dissolved organic matter (DOM) samples collected from the Adour estuary along a salinity gradient were imaged by TEM. The average size of the SRHA measured by PCS increased with pH and ionic strength. This behavior was confirmed by TEM micrographs. The increase in pH and CaCl₂ engendered aggregation of the SRHA. Two aggregation steps were identified, a big increase in HS size occurred for small changes in CaCl₂ concentrations in the range <0.02 M CaCl₂, and a slight increase occured for higher concentrations in the range >0.02 M CaCl₂. The parallel analysis of SRHA by PCS and TEM allowed overcoming the limits for both techniques.Comparable results were found for the DOM samples from the Adour estuary (South West of France). The conformation and size of the HS network of these samples varied with the salinity gradient. TEM images demonstrated that, HS have a branched open network in freshwater whereas they have a more compacted and close network with increasing salinity.     

明胶膜的性能研究进展

明胶膜具有良好的生物相容性和可降解性,并且其物化性质能被调节,因而应用比较广泛.本文综述了不同添加剂和制备条件对明胶膜的机械性能、阻隔性能、生物可降解性等的影响.通常增塑剂可以改善明胶膜的脆性,减小其机械强度和热稳定性.交联能有效提高明胶膜的机械性能和热稳定性,减缓明胶的降解速率.交联包括化学交联、生物相容性交联和物理交联.明胶与蛋白质、糖类、脂类复合,其性能得以改进,并且将明胶与高聚物共混、共聚改性,可以改善明胶膜的性能以满足不同领域的应用.     

Cure reaction and phase behavior of liquid crystalline epoxides-anhydride systems

A series of novel liquid crystalline epoxides with lateral substituents were cured with anhydrides and the cure kinetics was investigated by non-isothermal DSC technique. The results showed that the lengths of lateral substituents have great effect on the value of Ea. The curing reaction became less active, when the liquid crystalline epoxides have long lateral substituents and were controlled by diffusion at the late stage of cure. A nematic structure was observed by POM and XRD.     

F-T合成Fe/Cu/K/Al2O3催化剂的结构性质、还原及碳化行为

采用连续共沉淀与喷雾干燥成型技术相结合的方法制备了微球状Fe/Cu/K/Al2O3催化剂, 结合TG、N2物理吸附、XRD、H2-TPR、CO-TPR、Mossbauer谱等表征手段, 研究焙烧温度对Fischer-Tropshc (F-T)合成铁基催化剂的结构性质、还原行为和碳化行为的影响. 结果表明, 较高的焙烧温度有利于碳酸盐的分解和结晶水的脱除, 促进了催化剂的还原. 随着焙烧温度的进一步升高, 催化剂的比表面积减小, 平均孔径增大, α-Fe2O3晶粒的粒径增大, 催化剂中金属与载体的相互作用增强, 从而削弱了CuO、K2O助剂的作用, 严重抑制了催化剂的还原和碳化.