Das Reaktionsverhalten von Cp2NbCl2 gegenüber WF6—Struktur von [Cp2NbCl2]4[WF6]2[WCl6]

The oxidation of Cp₂NbCl₂ with pure WF₆ in SO₂ solution yielded the cationic metallocene species [Cp₂NbCl₂]⁺[WF₆]⁻ essentially in quantitative yield. The same reaction carried out in the presence of either equimolar amounts or a two-fold excess of HCN led to the preparation of the new niobocenium salt [Cp₂NbCl₂]₄⁺[WF₆]²⁻ which was studied by single crystal X-ray diffraction. This compound represents the first example of a structurally characterized metallocene-WF₆⁻ complex, and crystallizes in the tetragonal system: space group, P4₁2₁2(No. 92), a = 11.083(8) Å, c = 48.285 (9) Å; Z = 8; R = 0.0759, R_W = 0.0841. ab]Die Oxidation von Cp₂NbCl₂ mit reinem WF₆ führt in SO₂-Lösung zur Synthese von [Cp₂NbCl₂ ]⁺[WF₆]⁻ in nahezu quantitativer Ausbeute. Die analoge Reaktion führt unter Anwesenheit der äquimolaren Menge oder eines zweifachen Überschusses an HCN zur Ausbildung des Niobocenium-Komplexsalzes [Cp₂NbCl₂]₄⁺ [WF₆]₂⁻[WCl₆]²⁻, von dem eine Röntgenstrukturanalyse angefertigt wurde. Diese Verbindung repräsentiert den ersten structurell charakterisierten Vertreter eines Metallocen-WF₆⁻-Komplexes und kristallisiert im tetragonalen System: Raumgruppe P4₁2₁2 (Nr. 92), a = 11.083(8) Å, c = 48.285(9) Å; Z = 8; R = 0.0759, R_W = 0.0841. kw]Niobium; X-ray diffraction; Oxidation; Metallocenes     

MOLECULAR CLOSE-PACKING METHOD AND ITS APPLICATION TO CRYSTAL STRUCTURE DETERMINATION OF DESHEXAPEPTIDE (B25--B30) INSULIN

Based on the molecule-packing theory, we defined a molecule-packing function express-ing the compatibility of packing among the symmetry-related molecules in a unit cell. Acomputer program imitating the close-packing of molecules in the objective crystal latticeand giving the function value of each rotation and translation of the molecule in the unitcell was performed, and it therefore made the close-packing of molecules expressquantitatively. This method not only could judge a correct solution from several peaks ofthe rotation or translation function but it may also independently, quantitatively and quicklysolve some specific problems of rotation and translation. Using known structure of despenta-peptide (B26--B30) insulin as an example, the effectiveness of this method and its programwas inspected, and this method was successfully applied to solving the translation problem ofthe unknown structure of deshexapeptide (B25--B30) insulin. The molecular close-packingmethod proved by the results of R--search     

Photochemistry and photopolymerization activity of novel perester derivatives of fluorenone: a conventional and laser flash photolysis study

The photochemistry of three novel t-butylperester derivatives of fluorenone was examined and compared with unsubstituted fluorenone and a mono-t-butylperester of benzophenone using both conventional microsecond and nanosecond laser flash photolysis. On conventional microsecond flash photolysis in 2-propanol, all four fluorenone compounds gave transient absorption in the region 300–400 nm due to a ketyl radical formed from the abstraction of a hydrogen atom from the solvent by the upper excited triplet n—π* state of the fluorenone chromophore. This assignment was confirmed by a pH-dependent study on the transient absorption spectra. The nitro-t-butylperester derivative of fluorenone gave additional absorption above 400 nm due to species associated with the nitro group. No evidence for benzoyloxy radical formation could be found in non-hydrogen-atom-donating solvents with microsecond flash photolysis which is associated with homolysis of the perester groups. On nanosecond laser flash photolysis of the fluorenone compounds at 355 nm excitation in acetonitrile and hexa-fluorobenzene, transient absorptions were observed in the region 320–640 nm due to the corresponding triplet states. All the t-butylperester derivatives showed residual absorbances at longer time delays which were tentatively assigned to the corresponding benzoyloxy radicals produced by homolysis of the perester groups. In contrast, the mono-t-butylperester of benzophenone, included for comparison only, showed very weak transient absorption in the region 320–640 nm compared with that of the strong triplet of benzophenone under the same excitation conditions. The triplet absorptions and lifetimes of the fluorenone compounds were correlated with their photopolymerization activities in bulk methylmethacrylate monomer. In oxygenated solutions, the triplet absorptions of fluorenone and benzophenone were effectively quenched; however, long-lived transient growths were observed for all the t-butylperester derivatives. The intensities of these novel transient absorptions appear to correlate with the total number of t-butylperester groups in the fluorenone molecule and tentative assignments are discussed.     

THE EFFECT OF PHOTO-CROSSLINKING ON THE ORIENTATION STABILITY OF POLYVINYL ALCOHOL CONTAINING 4-NITRO-4′-ALKOXYSTILBENE AND CINNAMYL PENDENT GROUPS*

Crosslinking is one of the effective routes for improving the orientation stability of poledpolymer films. The derivative of polyvinyl alcohol containing 4-nitro-4'-alkoxystilbene andphoto-crosslinkable cinnamyl groups as side chains has been synthesized. The in-situ simul-taneous photo-crosslinking poling of synthesized polymer films has been performed. Thesecond order nonlinear optical coefficient d_(33) of poled film is 11 pm/V. The SHG mea-surements show that the break-over temperature of SHG signal is raised obviously afterirradiation, its orientation stability is doubled as compared with that of non-crosslinkingsamples.     

Preparation and characterization of vanadium(IV) oxide supported on SBA-15 and its catalytic performance in benzene hydroxylation to phenol using molecular oxygen

Preparation of dispersed transition metal oxides catalyst with low oxidation state still remains a challenging task in heterogeneous catalysis.In this study,vanadium oxides supported on zeolite SBA-15 have been prepared under hydrothermal condition using V 2 O 5 and oxalic acid as sources of vanadium and reductant,respectively.The structures of samples,especially the oxidation state of vanadium,and the surface distribution of vanadium oxide species,have been thoroughly characterized using various techniques,including N 2-physisorption,X-ray diffraction(XRD),transmission electron microscopy(TEM),X-ray photoelectron spectroscopy(XPS),UV-visible spectra(UV-Vis) and UV-visible-near infrared spectra(UV-Vis-NIR).It is found that the majority of supported vanadium was in the form of vanadium(IV) oxide species with the low valence of vanadium.By adjusting hydrothermal treatment time,the surface distribution of vanadium(IV) oxide species can be tuned from vanadium(IV) oxide cluster to crystallites.These materials have been tested in the hydroxylation of benzene to phenol in liquid-phase with molecular oxygen in the absence of reductant.The catalyst exhibits high selectivity for phenol(61%) at benzene conversion of 4.6%,which is a relatively good result in comparison with other studies employing molecular oxygen as the oxidant.     

Salt effect on molecular orientation at air/liquid methanol interface

The salt effects on molecular orientation at air/liquid methanol interface were investigated by the polarization-dependent sum frequency generation vibrational spectroscopy(SFG-VS). We clarified that the average tilting angle of the methyl group to be u = 308 58 at the air/pure methanol surface assuming a d-function orientational distribution. Upon the addition of 3 mol/L Na I, the methyl group tilts further away from the surface normal with a new u = 418 38. This orientational change does not explain the enhancement of the SFG-VS intensities when adding Na I, implying the number density of the methanol molecules with a net polar ordering in the surface region also changed with the Na I concentrations. These spectroscopic findings shed new light on the salt effects on the surfaces structures of the polar organic solutions. It was also shown that the accurate determination of the bulk refractive indices and Raman depolarization ratios for different salt concentrations is crucial to quantitatively interpret the SFG-VS data.     

Phase-field modeling of void evolution and swelling in materials under irradiation

Void swelling is an important phenomenon observed in both nuclear fuels and cladding materials in operating nuclear reactors. In this work we develop a phase-field model to simulate void evolution and void volume change in irradiated materials. Important material processes, including the generation of defects such as vacancies and self-interstitials, their diffusion and annihilation, and void nucleation and evolution, have been taken into account in this model. The thermodynamic and kinetic properties, such...     

浙江省城镇建设用地空间扩展时空特征分析

运用1990~2015年浙江省6期土地利用数据, 使用扩展速率、扩展强度、分形维数等指标分析浙江省城镇建设用地空间格局. 结果表明 (1)1990~2015年, 浙江省城镇建设用地增长在5个时期呈现“W”趋势, 从不同行政等级来看, 扩展速度的发展趋势具有一致性, 2000~2005年是浙江省不同行政等级的城市城镇用地扩展速度的最快阶段. (2)从扩展强度来看, 浙江省在2000~ 2005年对城镇用地扩展最大, 其他时期基本维持稳定. 地势平缓的城市往往开发强度大, 丘陵地区的城市处于缓慢扩展阶段. (3)浙江省城镇用地空间结构的分形维数和稳定性特征存在波动性. 城镇用地的空间结构特征与城镇用地增长过程和发展阶段具有一定的联系. (4)浙江省城镇用地重心受到地形限制明显. 西南地区受到丘陵地形影响, 重心移动方向大多数与斜长的峡谷平行; 北部平原区域的城镇用地的重心变化往往受到经济等社会因素影响较大. (5)浙江省城镇建设用地空间扩展的影响因素上存在一定规律, 可看出1995年、2010年、2015年主要倾向于社会经济的影响, 在2000年、2005年则倾向于自然因素的影响.     

2型糖尿病并发大血管病变的危险因素分析与自我管理

探讨2型糖尿病合并大血管病变的相关危险致病因素, 以期指导制定自我管理方案. 采用回顾性病例-对照研究方法, 选2型糖尿病患者85例, 根据是否合并大血管病变, 分为单纯2型糖尿病组(T2DM组, n=41)及合并大血管病变组(T2DM+MV组, n=44), 选同期的40例非糖尿病患者作为对照, 比较各组患者的一般资料及入院时的血压、血清镁、空腹血糖、糖化血红蛋白和血脂水平等参数. 结果表明 糖尿病病程(比值比(OR)=1.268, 95%置信区间(CI) 1.076~1.496)、空腹血糖(OR=2.147, 95% CI 1.167~3.949)及糖化血红蛋白水平(OR=4.936, 95% CI 1.575~15.470)是2型糖尿病患者并发大血管病变的独立危险因素, 而血清镁水平则是独立保护性因素(OR=0.001, 95% CI 0.000~0.014). 同时表明, 在2型糖尿病早期自我管理中, 积极控制血糖及维持血清镁在较高水平是预防大血管病变的有效途径.     

文化创意企业视角的长三角城市网络演变特征

运用社会网络与位序-规模法分析长江三角洲地区16市上市类文化创意企业的母-子公司数据信息, 揭示文化创意企业集聚视角长三角城市网络结构及其演变特征. 研究发现: (1) 2005~2015年, 长三角地区文化创意企业上市公司总部数量逐年增加, 公司总部多设立于上海、杭州、苏州以及南京4地; (2)传媒类和软件及计算机类企业多分布于传统区域, 设计咨询类企业生产网络中, 存在传统非核心城市跃升为区域核心城市的现象; (3)上市公司生产网络结构逐渐复杂, 多中心及新核心相继出现, 且生产网络中城市位序有变动趋势, 文化创意产业空间动态正形塑城市体系结构. 为此, 建议长三角文化创意企业发展中应加强企业母子间的联系强度, 促进城市创意流动网络化, 有望推进长三角创意源-流形塑创意城市群新体系.