戊烯自由基阳离子的密度泛函理论研究

使用密度泛函理论B3LYP方法和6-31G(d,p)、6-31＋G(d,p)、6-311G(d,p)及6-311＋G(d,p)基组，分别对2-C5H10＋和1-C5H10＋的各种构象进行了几何构型优化，并用B3LYP/6-311G(d,p)进行了频率分析计算.计算预言1-C5H10＋具有非平面构型，与以往报导的从头算计算结论相反.在两个自由基阳离子的各种构象的B3LYP几何构型上，进行了B3LYP和UMP2(full)方法的超精细偶合常数计算，得到了比以往更好的结果.     

Tailoring the optical property by a three-dimensional epitaxial heterostructure: a case of ZnO/SnO2

Epitaxial growth, as a best strategy to attain a heterostructure with a well-defined and clean interface, usually takes place on a planar substrate. In this paper, using a ZnO/SnO2 core-shell heterostructure as an example, we demonstrate the possibility of establishing a three-dimensional epitaxial interface between two materials with different crystal systems for the first time and show possible tailoring optical properties by building the heteroepitaxial crystal interface. The characterization results of element mapping, high-resolution transmission electron microscopy, and selected area electric diffraction reveal that the as-prepared ZnO/SnO2 heterostructure has a tetrapod-like ZnO core and a SnO2 shell with 15-30 nm, and their special epitaxial relation is (010)SnO2//(010)ZnO and [100]SnO2//[0001]ZnO. Such three-dimensional epitaxy between the ZnO core and SnO2 shell is quite different from the usual planar epitaxy or three-dimensional epitaxy between materials having the same crystal structure. A rational model of such complicated epitaxy has been proposed through investigating the certain structural comparability between the wurtzite ZnO and rutile SnO2 crystals. The as-prepared T-ZnO/SnO2 epitaxial heterostructure exhibits unique luminescence properties in contrast with individual tetrapod ZnO and SnO2 nanostructures, in which the epitaxial interface induces new luminescence properties. This result may inspire great interest in exploring other complicated epitaxy systems and their potential applications in laser, gas sensor, solar energy conversion, photo catalysis, and nanodevices in the future.     

Palladium-benzimidazolium salt catalyst systems for Suzuki coupling: development of a practical and highly active palladium catalyst system for coupling of aromatic halides with arylboronic acids

Palladium-benzimidazolium salt catalyst systems have been studied for the Suzuki coupling. A different substitutent effect has been uncovered with respect to nitrogen substituents in the benzimidazolium salts from the palladium-imidazolium salt analogs. A practical and highly active palladium catalyst system, PdCl₂/N,N′-dibenzylbenzimidazolium chloride 2, has been identified for the Suzuki coupling of aromatic halides with arylboronic acids. The coupling of a wide array of aromatic halides with arylboronic acids with the PdCl₂-2 catalyst system gave good to excellent yields. The effective palladium loading could be as low as 0.0001 mol% and 0.01-0.1 mol% for iodide and bromide substrates, respectively. The coupling of unactivated aromatic chlorides with arylboronic acids also gave good results using Cs₂CO₃ as base with a 2 mol% palladium loading. The electronic factors from aromatic halides exert a significant influence on the Suzuki coupling catalyzed by the PdCl₂-2 system while the electronic effect from the arylboronic counterparts is negligible. The aromatic halides with modest steric hindrance could also couple smoothly with phenylboronic acids using the PdCl₂-2 catalyst system.     

Pore morphologies in disordered nanoporous thin films

Materials with nanometer size heterogeneities are commonplace in the chemical and biological sciences (e.g, polymer blends, microemulsions, gels) and often exhibit complex morphologies. Although this morphology has a dramatic effect on the materials' properties, it is often difficult to accurately characterize. We describe a method, using small-angle X-ray scattering data, of generating representative three-dimensional morphologies of isotropic two-phase materials where the morphology is disordered, and we apply this to thin films containing nanometer sized pores with a range of porosities (4-44%). These representations provide a visualization of the pore morphology, give the pore size scale and extent of interconnection, and permit the determination of the transitions from closed pore to interconnected pores to bicontinuous morphology.     

Polarographic Behavior of Bivalent Germanium in Alkaline Solution

Bivalent germanium was polarographically studied in sodium hydroxide solution at various concentrations. A well-defined reduction wave with half-wave potential varying from ?0.90 to ?0.98 volt vs. S.C.E. was observed for 1×10^?4 M Ge(II) in concentration range of 0.2 to 2.0 F with respect to NaOH, and from ?0.70 to ?0.88 volt vs. S.C.E. in the pH range 9.0–12.1 at 25°. The value of i_d/C is 5.43 μα/mM and that of i_d/C m^for t^1/8 is 5.21. Dependence of E_1/2 upon pH is expressed by —E_1/2 =0.18+0.058 pH. Experimental result suggests that the reaction proceeds in two-steps involving an irreversible two-electron reduction: Ge(OH)₂+OH^?→HGeO₂^?+H₂O and HGeO₂^?+H₂O+2e→Ge⁰+3OH^?.     

环状芴基张力半导体拉曼光谱理论与实验研究

环状芴基张力半导体由于其特殊的分子结构，发射状排布的p轨道和纳米级空腔等诸多特点，引起了科学家广泛的关注.相对于直链型芴基半导体，环状芴基张力半导体展现出独特的光电性质.然而，迄今为止其振动性质没有被报道.对四元环芴的晶体与直链四聚芴粉末样品进行拉曼光谱表征和归一化处理，并结合理论计算.结果表明，与直链寡聚芴相比，环芴类似于碳纳米管的G峰发生了偏移，并且低频区域拉曼频移峰的峰强增加.其原因是由于张力的引入，改变了芴基主链的骨架和电子结构，加强芴骨架上π电子离域，同时使环芴中每个芴单元都参与到振动中.该研究结果为芴基张力半导体材料拉曼光谱的研究提供了一定的工作基础.     

Force acting on the microparticles in electrorheological solids under the application of a nonuniform ac electric field

Under the application of electric fields, the structure of electrorheological (ER) solids can be changed from the body-centered tetragonal lattice to other lattices. We have derived the dipole factor for the lattice by taking into account the local-field effect through the Ewald–Kornfeld formulation, and expressed it in the spectral representation exactly. It is found that when the ER solid is subject to a nonuniform ac electric field, the force acting on the microparticle can be affected by the structure transformation, and local-field effect as well as field frequency. Our results are very well understood in the spectral representation theory.     

Effects of pressure pulsation on oxygen transfer rate measured by sulfite method

Pressure pulsation (PP) was investigated for its effects on oxygen transfer rate (OTR) measured by sulfite oxidation. By manipulating airflow rate, 0.41–1.2 vvm, and a control valve in a 4-L bioreactor, the frequency of PP was varied at different gas pressures3–15 psig. A mathematical model of OTR was built and compared to experimental data. OTR was also examined at constant gas pressure, 4.5–15.0 psig. The results indicate a good agreement between measurement and model prediction. OTR above 9 psig during PP showed significant enhancement at 25°C. This proves that PP not only affects the elevation of DO level, but also increases the interfacial area and mass transfer coefficient.     

用透射电镜和火焰原子吸收法分析大气总悬浮颗粒物

以大气总悬浮颗粒物为主要研究对象,用透射电镜观察其形貌,污染特征明显;用火焰原子吸收法测定其水溶性常规元素K、Na、Ca和Mg。K、Na、Ca和Mg的检出限分别为0.105、0.124、0.259和0.237mg/kg,线性相关系数不低于0.9979,加标回收率为90.0%～95.0%,测定结果的相对标准偏差为0.6%～2.1%(n=6)。     

二氧化碳/环氧丙烷/γ-丁内酯三元共聚物微球降解性的研究

动物体内的体液和肠胃等器官的环境各不相同，这就要求各种不同用途的载药体的降解性能必须满足特定环境的要求。同时，可降解材料在不同的降解介质中通常有着不同的降解表现，这也决定着可降解材料的运用环境。因此，有必要对降解性材料在不同降解介质中的降解性进行专门的研究，由CO2和环氧化物合成的脂肪族聚碳酸酯具有良好的生物降解性能。