Poly[μ‐aqua‐μ4‐naphthalene‐1,8‐dicarboxylato‐zinc(II)]

In the title complex, [Zn(C₁₂H₆O₄)(H₂O)]_n, a Zn^II polymer based on naphthalene‐1,8‐dicarboxylate (1,8‐nap), the Zn^II atoms adopt an elongated octahedral coordination geometry. A zigzag chain is formed by μ₂‐aqua ligands and μ₂‐carboxylate groups of the 1,8‐nap ligands. Adjacent parallel chains are further linked by 1,8‐nap ligands, forming a twisted two‐dimensional layer structure along the (100) plane.     

甲基环戊二烯基希土二氯化物Cp′LnCl2·3THF(Ln=Sm-Er,Y)的合成和表征

本文通过无水三氯化希土与等摩尔的甲基环戊二烯基钠(Cp′Na)在四氢呋喃(THF)中反应，合成了八个新的中性甲基环戊二烯基希土二氯化合物Cp′LnCl₂·3THF［Ln=Sm(1), Eu(2), Gd(3), Tb(4), Dy(5), Ho(6), Er(7), Y(8)］，并研究了茂环上甲基取代基对一茂二氯希土配合物分子结构及稳定性的影响。元素分析、红外光谱和质谱鉴定结果表明这八个化合物都是溶剂化的单体结构，其中配合物7的结构还用单晶X射线分析确证。     

A New Kind of Void Soap-free P（MMA-EA-MAA） Latex Particles

Soap-flee P(MMA-EA-MAA) particles with narrow size distribution were synthesized by seeded emulsion polymerization of methyl methacrylate (MMA), ethyl acrylate (EA) and methacrylic acid (MAA), and large voids inside the particles were generated by alkali posttreatment in the presence of 2-butanone. Results indicated that the size of void and theparticle volume were related with the amount of 2-butanone. The generation mechanism of voids was proposed.     

Reaction of porous silicon with both end-functionalized organic compounds bearing alpha-bromo and omega-carboxy groups for immobilization of biomolecules

Both end-functionalized (alpha-bromo and omega-carboxy) compounds were first tested for the radical reaction on the silicon-hydride (Si-H) terminated porous silicon (PSi) with/without the presence of diacyl peroxide initiator under microwave irradiation. Then the carboxylic acid monolayers (CAMs) assembled on PSi through the robust Si-C bonds were converted to amino-reactive linker, N-hydroxysuccinimide (NHS)-ester, terminated monolayers. And finally two proteins of bovine serum albumin (BSA) and lysozyme (Lys) were immobilized through amide bonds. The optimum PSi membrane for protein immobilization without collapse, with parameters of porous radii 4-10 nm and depth 0.2-4.6 mum, was prepared from the (100)-oriented p-type silicon wafer. The chemically converted surface products were monitored with Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and field emission scanning electron microscopy (FESEM).     

Systematic synthesis and characterization of single-crystal lanthanide orthophosphate nanowires

A simple hydrothermal method has been developed for the systematic synthesis of lanthanide orthophosphate crystals with different crystalline phases and morphologies. It has been shown that pure LnPO(4) compounds change structure with decreasing Ln ionic radius: i.e., the orthophosphates from Ho to Lu as well as Y exist only in the tetragonal zircon (xenotime) structure, while the orthophosphates from La to Dy exist in the hexagonal structure under hydrothermal treatment. The obtained hexagonal structured lanthanide orthophosphate LnPO(4) (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, and Dy) products have a wirelike morphology. In contrast, tetragonal LnPO(4) (Ln = Ho, Er, Tm, Yb, Lu, Y) samples prepared under the same experimental conditions consist of nanoparticles. The obtained hexagonal LnPO(4) (Ln = La --> Tb) can convert to the monoclinic monazite structured products, and their morphologies remained the same after calcination at 900 degrees C in air (Hexagonal DyPO(4) is an exceptional case, it transformed to tetragonal DyPO(4) by calcination), while the tetragonal structure for (Ho--> Lu, Y)PO(4) remains unchanged by calcination. The resulting LnPO(4) (Ln = La --> Dy) products consist almost entirely of nanowires/nanorods with diameters of 5-120 nm and lengths ranging from several hundreds of nanometers to several micrometers. Europium doped LaPO(4) nanowires were also prepared, and their photoluminescent properties were reported. The optical absorption spectrum of CePO(4) nanowires was measured and showed some differences from that of bulk CePO(4) materials. The possible growth mechanism of lanthanide phosphate nanowires was explored in detail. X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy, electron diffraction, infrared absorption spectra, X-ray photoelectron spectroscopy, optical absorption spectra, and photoluminescence spectra have been employed to characterize these materials.     

Rhenium-promoted diastereo- and enantioselective cyclopentannulation reactions: furans as 1,3-propene dipoles

The rhenium furan complexes TpRe(CO)(MeIm)(eta2-2-methylfuran) (1) and TpRe(CO)(MeIm)(eta2-2,5-dmethylfuran) (2) undergo Lewis acid-promoted cyclopentannulation reactions with enones and enals to generate 3-acetylcyclopentene complexes. During the reaction, a rearrangement occurs such that the alpha and beta carbons of the enone are incorporated into the new carbocycle. Treatment of these complexes with an oxidant (H2O2 or silver triflate) liberates the acetylcyclopentene. When a resolved form of the rhenium complex is used, the acetylcyclopentenes can be obtained enantioselectively.     

新型化合物[Ni(en)3]2[Ni(en)2(H2O)2][As6V15O42]·4H2O晶体的水热合成与表征

金属氧酸盐因其在医药临床、工业催化、功能材料等方面的广泛应用而引起人们的关注[1～6], 其中, 有关钒化学的研究一直很活跃, 钒具有与钼、钨明显不同的结构特性, 钒可以采取VO4, VO5和VO6方式配位, 同时, 钒的价态可以是+3, +4和+5价. 由于钒可采取多种配位方式及多种价态, 与钼酸盐和钨酸盐相比, 钒酸盐更具有结构柔顺性, 同时易形成低价或混合价态物种.在以往的文献中, 有关P-V-O体系多金属氧酸盐的水热合成的研究已有大量的报道[7], 在常规溶液合成中, 人们已对As-V-O体系进行了相对深入的研究, 而有关水热合成的研究报道却很少, 已见报道的砷钒化合物有K6*6H2O[8,9], 4-[10], 6-[11](X=SO2-3, SO2-4, H2O). 为了探究水热条件下As-V-O体系的反应特性, 我们开展了这方面的研究工作, 并取得了突破性进展. 本文采用中温水热技术合成了含有机基团的砷矾超分子化合物2**4H2O, 探讨这类化合物的非线性光学性质、催化性质及其它功能特性将是一个非常有意义的研究领域.     

青海柴达木地区植物白刺叶中微量元素特征

青海柴达木地区分布有丰富的白刺植物资源。利用220FS原子吸收光谱仪分析了该地区三种白刺叶片的Cu,Zn,Fe,Mn,Cr,Ni,Cd等微量元素。结果表明，铬、 锰含量显著提高是青海柴达木地区植物白刺叶资源微量元素特征。这为柴达木地区白刺叶资源的开发利用提供科学依据。     

Geometries,vibrational frequencies,and electron affinities of X2Cl (X=C,Si,Ge) clusters

Ab initio quantum chemical calculations have been performed on X₂Cl^? and X₂Cl (X = C, Si, Ge) clusters. The geometrical structures, vibrational frequencies, electronic properties and dissociation energies are investigated at the Hartree–Fock (HF), Møller–Plesset second‐ and fourth‐order (MP2, MP4), CCSD(T) level with the 6‐311+G(d) basis set. The X₂Cl (X = C, Si, Ge) and X₂Cl^? (X = Si, Ge) take a bent shape obtained at the ground state, while C₂Cl^? has a linear structure. The impact on internal electron transfer between the X₂Cl and the corresponding anional clusters is studied. The three different types of electron affinities (EAs) at the CCSD(T) are reported. The most reliable adiabatic electronic affinities, obtained at the CCSD(T)/cc‐pvqz level of theory, are predicted to be 3.30, 2.62, and 1.98 eV for C₂Cl, Si₂Cl, and Ge₂Cl, respectively. The calculated EAs of C₂Cl and Ge₂Cl are in good agreement with theoretical results reported. The correlation effects and basis sets effects on the geometrical structures and dissociation energies are discussed. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

氢气对氯硅烷功能化非共轭α,ω-双烯烃和丙烯共聚物链结构的影响

基于Ziegler-Natta催化剂的氯硅烷功能化非共轭α,ω-双烯烃与丙烯共聚,在水的引发下脱水缩合可有效地形成长支链结构的聚丙烯树脂.而氢气常作为丙烯聚合中的链转移剂,调控聚丙烯的分子量,基于此,研究了氢气对氯硅烷功能化非共轭α,ω-双烯烃与丙烯共聚物链结构的影响.核磁共振氢谱(~1H-NMR)测试结果表明,氢气抑制了氯硅烷功能化非共轭α,ω-双烯烃的插入,随着氢气用量的增加,共聚物分子链中端基乙烯基含量由0.12 mol%降低到0.05 mol%.熔体流变行为测试结果显示,聚合物熔体的储能模量、损耗模量和零剪切黏度均随着氢气用量增加而降低,这主要是由于相对分子质量减小和长支链密度的减少.