Hartree–Fock and density functional theory study of remote substituent effects on gas‐phase heterolytic Fe–O and Fe–S bond energies of p‐G‐C6H4OFe(CO)2(η5‐C5H5) and p‐G‐C6H4SFe(CO)2(η5‐C5H5)

The knowledge of accurate bond strengths is a fundamental basis for a proper analysis of chemical reaction mechanisms. Quantum chemical calculations at different levels of theory have been used to investigate heterolytic Fe–O and Fe–S bond energies of para‐substituted phenoxydicarbonyl(η⁵‐cyclopentadienyl) iron [p‐G‐C₆H₄O(η⁵‐C₅H₅)Fe(CO)₂, abbreviated as p‐G‐C₆H₄OFp ( 1 ), where G = NO₂, CN, COMe, CO₂Me, CF₃, Br, Cl, F, H, Me, MeO, and NMe₂] and para‐substituted benzenethiolatodicarbonyl(η⁵‐cyclopentadienyl) iron [p‐G‐C₆H₄S(η⁵‐C₅H₅)Fe(CO)₂, abbreviated as p‐G‐C₆H₄SFp ( 2 )] complexes. The results show that BP86 and TPSSTPSS can provide the best price/performance ratio and more accurate predictions in the study of ΔH_het(Fe–O)'s and ΔH_het(Fe–S)'s. The excellent linear free‐energy relations [r = 0.99 (g, 1a), 1.00 (g, 2b)] among the ΔΔH_het (Fe–O)'s and Δpk_a's of O–H bonds of p‐G‐C₆H₄OH or ΔΔH_het(Fe‐S)'s and Δpk_a's of S–H bonds of p‐G‐C₆H₄SH imply that the governing structural factors for these bond scissions are similar. And the linear correlations [r = ?0.99 (g, 1g), ?0.98 (g, 2h)] among the ΔΔH_het (Fe‐O)'s or ΔΔH_het(Fe‐S)'s and the substituent σ_p^? constants show that these correlations are in accordance with Hammett linear free‐energy relationships. The polar effects of these substituents and the basis set effects influence the accuracy of ΔH_het(Fe–O)'s or ΔH_het(Fe–S)'s. ΔΔH_het(Fe–O)'s(g) ( 1 ) and ΔΔH_het(Fe–S)'s(g)( 2 ) follow the Capto‐dative principle. The substituent effects on the Fe–O bonds are much stronger than those on the less polar Fe–S bonds. Insight from this work may help the design of more effective catalytic processes. Copyright © 2013 John Wiley & Sons, Ltd.     

花状TiO2分级结构的可控合成与其光催化性能

采用水热法可控合成了花状TiO₂分级结构材料,运用扫描电镜、透射电镜、X射线衍射、N₂物理吸附-脱附等手段,对其进行了表征,系统研究了NaOH用量、H₂O₂浓度、HNO₃浓度、反应温度及时间等因素对所得样品形貌的影响,并评价了它们的光催化性能.结果表明,花状TiO₂分级结构为锐钛矿相,颗粒大小均一;随制备条件的变化,构成花状TiO₂分级结构的基元结构分别为纳米线、纳米片,纳米线直径约25nm,纳米片厚度不足10nm;该样品具有较高的比表面积,表现出良好的单次光催化活性与重复使用性能.     

高光谱分析叶菜对颗粒物污染的响应特征规律

大气中的颗粒物不仅影响人类生活,还影响植物的光合作用、生长发育和产量品质。实现了颗粒物污染环境的人工模拟,并对采收期的小白菜、生菜、小油菜三种叶菜进行颗粒物作用试验,获取叶片的光合生理信息和高光谱数据,基于高光谱技术和植物表型分析叶菜对颗粒物的响应机理,研究叶菜的光合特性和光谱特征对颗粒物污染的响应情况。结果表明：以颗粒物作为唯一差别条件下,三种叶菜叶片的高光谱曲线整体趋势相同,在可见光波段内试验组反射率增加最大,红边位置发生蓝移,小油菜对颗粒物的作用最敏感,小白菜吸附颗粒物的能力最强。分别比较三种叶菜的净光合速率与叶片原始光谱、一阶导数光谱的相关性,利用相关分析法提取三种叶菜的敏感波段,用原始光谱、FD、MSC和相关分析法提取特征波长;比较10个高光谱特征参数及4个植被指数与净光合速率的相关系数,选出敏感光谱特征参数和植被指数,即生菜的Dr,SDr,SDr/SDb和SDr/Sdy,小白菜的SDr,Dy,NIRRP,(SDr-SDy)/(SDr+SDy)以及小油菜的λr,SDy,(SDr-SDy)/(SDr+SDy)。用ln对数运算、多项式函数以及几种组合方法建立三种叶菜叶片的净光合速率定量反演模型,其中,预处理方法采用SG,FD,SD和MSC,建模方法采用CLS,PLS,PCR和SMLR。以相关系数为模型评价指标,最终确定FD+SG+PLS方法是建立生菜和小白菜净光合速率反演模型的最优方法,FD+SG+MSC+SMLR方法是建立小油菜净光合速率反演模型的最优方法。所建模型可为今后颗粒物污染环境下的模型修正提供参考,具有实用性。研究结果为利用高光谱技术研究叶菜类蔬菜在颗粒物污染环境下的诊断与分析提供理论依据,为设施农业蔬菜的病害预警、生理信息监测、设施环境的净化和管控提供新思路。     

广义凸空间上重合点定理和极大极小不等式

利用已知的KKM型定理,在广义空间上得到若干个新的重合点定理和推广的Fan-Browder型不动点定理,并且讨论了Von Newmann-Sion型极大极小不等式.主要结果改进和推广了文献中的相应结论.     

对称空间中具有交换点的自映射族的惟一公共不动点

证明了对称空间中具有交换点的两个自映射满足一定条件时存在惟一公共不动点的定理.     

一般化凸空间上极大极小不等式及其应用

我们首先改进了已有的KKM型定理,然后根据改进后的KKM型定理得到了一般化凸空间上的KyFan型极大极小不等式,最后利用它给出了Fan-Kneser型不等式族及其一些应用.我们的结论对文献中的相应结果进行了改进和一般化。     

自模型曲线分辨法校正ICP-AES中谱线重叠干扰——测量误差对结果的影响

本文将自模型曲线分辨方法(SMCR)应用于ICP-AES谱线重叠光谱干扰的校正,并就测量误差对重叠光谱解析结果的影响作了详细的研究和讨论。两谱线的重叠程度越大,随机误差对光谱干扰校正的影响越大。对测量数据作平滑处理。可以减小数据随机误差对结果的影响,但平滑次数增加,将导致光谱图变形,使干扰校正结果产生较大的误差。数据的平滑不能减小光谱偏离加和性的误差。本工作对两条光谱重叠的情况作了讨论,并取得了较好的结果,表明SMCR法是校正ICP-AES中重叠谱线干扰的一种简便、快速的方法。     

非紧的一般化凸空间上不动点定理和supinfsup不等式

利用一般化凸空间上的KKM型定理得到有限交定理,然后作为应用讨论了在没有紧性限制的一般化凸空间上集值映射的不动点的存在问题以及Von Neumann-Fan型supinfsup不等式(等式)问题,最后给出了极大极小等式.     

Roles of polyacrylate dispersant in the synthesis of well-dispersed BaSO4 nanoparticles by simple precipitation

Well-dispersed BaSO4 nanoparticles were synthesized in the presence of sodium polyacrylate （PAAS） by a simple precipitation method, with BaCl2 and （NH4）2SO4 as reactants. The different roles performed by PAAS in the synthesis of BaSO4 nanoparticles were investigated using X-ray diffractometry, Fourier transform infrared spectroscopy, and transmission electron microscopy. The results indicate that the assynthesized BaSO4 nanoparticles were spheres with an average diameter of 30 nm and that their surfaces were affected by the PAAS. Under a typical procedure employed, PAAS reacted with BaCl2 to yield an intermediate, serving as a control releasing agent and separating the nucleation and crystal growth processes of the BaSO4 nuclei. During formation of the BaSO4 nanospheres, the intermediate slowly dissolved and released barium and polyacrylate ions, inhibiting the growth and aggregation of newly formed BaSO4 seeds and resulting in particles of narrow diameter distribution and improved dispersibility. Moreover, these polyacrylate ions further modified the surfaces of the BaSO4 nanoparticles.     

从Pleiades剖析新一代高性能小卫星技术发展

综述了著名的新一代极限性能高分辨小卫星Pleiades,说明了该卫星的技术特点,同时给出了其关键技术指标,并且有针对性地剖析了Pleiades在多星组网轨道设计、一体化超分辨焦平面设计、一体化综合电子学设计及敏捷姿态控制系统设计等方面所采用的先进技术和设计理念。在此基础上,提出了适应我国国情的小卫星新技术发展方向,包括CMOS TDI模式成像技术、高动态范围视频成像技术、基于可重构模块的柔性化集成技术、基于软件总线的星载软件设计技术以及星载一体化设计技术等,为今后我国研发具有更高的地面分辨率、在轨成像效率和成像质量的新一代高性能小卫星提供了新的思路。