TEOS-MTES基SiO2溶胶微结构的SAXS研究

正硅酸乙酯(TEOS)为前驱体,在碱性条件下制备含有无定形SiO2颗粒的溶胶,以甲基三乙氧基硅烷(MTES)在酸性条件下获得聚甲基硅氧链,二者混合后应用同步辐射X射线进行混合溶胶的SAXS散射强度测定,计算了溶胶的平均回转半径、平均粒径、两相界面层厚度、散射体体积分数、两相间比表面积等参数,辅以光子相关光谱法(PCS)和透射电子显微镜(TEM)观测溶胶粒度,证实SiO2颗粒被MTES混合物连接成族团.实验发现所测混合溶胶样品均表现出对Porod定理的负偏离,说明溶胶中颗粒与溶剂之间存在很明显的两相间界面层.     

Ab initio study of Rg2I− (Rg = Ar,Kr, Xe)

The equilibrium geometries, vibrational frequencies, and dissociation energies of rare gas iodine clusters Rg₂I^?(Rg = Ar, Kr, Xe) were calculated at the Hartree–Fock (HF), second‐order Møller–Plesset (MP2), the coupled cluster method with single and double excitation and a noniterative correction for triple excitations method [CCSD(T)] levels. The title species have bent C_2v structure of about 60° angle. The electron correlation effects and relativistic effects on the geometry and stability were investigated at CCSD(T) level. Both effects stabilize title species. The calculated electron affinities are in good agreement with the experimental results available. The effect of high angular momentum functions (g and h) was studied. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006     

新型除草剂及其杂质的LC-MS和GC-MS分析

High performance liquid chromatography (HPLC) and electrospray ionization mass spectrometry (ESI-MS) have been utilized to analyze the synthesized 2-(2-arylaminomethylphenoxy)pyrimidine derivatives, which are a new kind of environmentally benign herbicides and have passed the temporary pesticide registration. The identification of main product and impurities has been achieved according to the UV and mass spectra. Moreover, one impurity, introduced by the raw material in the last step of the synthetic route, was identified by GC-MS analysis. It can be concluded that the combination of chromatography and mass spectrometry, including LC-MS and GC-MS, provided a vital tool of the pesticide science.     

Synthesis of a tweezer-like bis(arylthiaalkoxy)calix[4]arene as a cation sensor for ion-selective electrodes: an investigation of the influence of neighboring halogen atoms on cation selectivity

Two novel tweezer-like 25,27-dihydroxy-26,28-bis(phenylthiaethoxy)calix[4]arenes 6 and 7 were synthesized by the reaction of 25,27-dihydroxy-26,28-bis(bromoethoxy)calix[4]arenes 3 and 4 for the evaluation of their ion-selectivity in ion-selective electrodes (ISEs). X-ray structural analysis indicated that calix[4]arene 7 is in an interesting infinite linear aggregate via self-inclusion. For investigation of the influences of substitutes on the behavior of the ISEs, the halogen substituted aryl analogues of 25,27-dihydroxy-26,28-bis(arylthiaethoxy)calix[4]arenes 8-12 were also synthesized and their ISE performances were evaluated under the same conditions. ISEs based on 6-12 as neutral ionophores were prepared, and their selectivity coefficients for Ag+ (log KAg,M(pot)) were investigated against other alkali metal, alkaline-earth metal, lead, ammonium ions and some transition metal ions using the fixed interference method (FIM). These ISEs showed excellent Ag+ selectivity over most of the interfering cations examined, except for Hg2+ having relative smaller interference (log KAg,Hg(pot) < or = 2.1). The 19F NMR spectra of 9 and 9.AgClO4 were recorded for investigation the fluorine environments in the complex. The 19F NMR spectra strongly suggested that the fluorine atoms on ionophore 9 participated in ligation with silver cation.     

DNA-templated self-assembly of protein and nanoparticle linear arrays

Self-assembling DNA tiling lattices represent a versatile system for nanoscale construction. Self-assembled DNA arrays provide an excellent template for spatially positioning other molecules with increased relative precision and programmability. Here we report an experiment using a linear array of DNA triple crossover tiles to controllably template the self-assembly of single-layer or double-layer linear arrays of streptavidin molecules and streptavidin-conjugated nanogold particles through biotin-streptavidin interaction. The organization of streptavidin and its conjugated gold nanoparticles into periodic arrays was visualized by atomic force microscopy and scanning electron microscopy.     

Two new C18-norditerpenoid alkaloids from Aconitum delavayi

Further phytochemical investigation of the unique C18-norditerpenoid alkaloids from the roots of Aconitum delavayi Franch ledto the isolation of two new norditerpenoid alkaloids,delavaconitine F 1 and delavaconitine G 2.Their structures were determinedfrom spectroscopic evidence.     

耐超高温SiC(Al)纤维先驱体——聚铝碳硅烷纤维的研究

以聚硅碳硅烷(PSCS)与乙酰丙酮铝(Al(AcAc)3)为原料,在常压高温条件下反应制备出聚铝碳硅烷(PACS),经过熔融纺丝制备了PACS纤维.应用GPC、IR、XPS、29Si-NMR、27Al-NMR、TG、SEM、元素分析和增重等一系列分析,分别对PACS纤维的微观组成、结构以及性能进行了分析.研究结果表明,以原料质量配比为6∶100(Al(AcAc)3∶PSCS)合成的PACS化学式为SiC2.0H7.5O0.13Al0.018,数均分子量为1700左右,最适宜制备PACS纤维;PACS纤维中主要存在SiC4、SiC3H等结构,同时存在Si—O—Al键;在氮气气氛中,PACS纤维的陶瓷产率达到52%左右;预氧化处理,PACS纤维中Si—H键与空气中的氧反应形成Si—O—Si交联结构,较聚碳硅烷(PCS)纤维易于氧化,经过预氧化的PACS纤维陶瓷产率达到80%左右,是制备耐超高温SiC(Al)陶瓷纤维的合适纤维;用预氧化PACS纤维制备的SiC(OAl)纤维和SiC(Al)纤维抗拉强度高,耐高温性能好.     

A New Chemo‐Enzymatic Route to Side‐Chain Liquid‐Crystalline Polymers: The Synthesis and Polymerization of 6‐(4‐Methoxybiphenyl‐4′‐oxy)hexyl Vinyl Hexanedioate

A novel synthetic method combining chemo and enzymatic synthesis strategies was employed to prepare a vinyl acetate type monomer, 6‐(4‐methoxybiphenyl‐4′‐oxy)hexyl vinyl hexanedioate (VA‐LC). Homo‐ and copolymers of VA‐LC with maleic anhydride (MAn) were prepared by conventional free radical polymerization using 2,2′‐azobisisobutyronitrile (AIBN) and 1,1′‐azobis (cyclohexane carbonitrile) (AHCN) as an initiator at 95 and 60 °C, respectively. The thermal properties of the generated polymeric material were investigated by differential scanning calorimetry (DSC), and the optical texture was inspected by polarizing optical microscopy (POM). While the monomer VA‐LC does not exhibit liquid‐crystalline properties, poly(VA‐LC), and the alternating copolymer of VA‐LC with maleic anhydride both displayed such properties.

     

Pheromones of coleoptera. Communication 6. Synthesis of R,Z-14-methyl-8-hexadecenal (cis-trogodermal)

Conclusions The simple synthesis of optically active R,Z-14-methyl-8-hexadecenal (cis-trogodermal), the principal components of the aggregation pheromone ofTrogoderma granarium, was accomplished. The synthesis was based on the use of R-1-bromo-4-methylhexane and Z-4-chloro-2-buten-1-ol as the sources of the chiral and olefin fragments.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 906–910, April, 1987.     

Fluorous reverse-phase silica gel-supported Lewis acids as recyclable catalysts in water

Fluorous reverse-phase silica gel (FRPSG)-supported Lewis acids which have fluorous ligands acted as effective catalysts of Baeyer-Villiger and Diels-Alder reactions in water. Direct esterification of carboxylic acid with alcohol in organic media was also catalyzed. The FRPSG-supported Lewis acids could be recycled by simple filtration after the reaction.