多酸有机亚胺衍生物的紫外-可见光谱及其取代基效应

以(Bu₄N)₄[α-Mo₈O₂₆]和各种取代苯胺及其盐酸盐为原料, 在碳二环己基亚胺(DCC)存在下, 经脱水反应,合成了多种六钼酸根有机亚胺衍生物, 并用元素分析,1H-NMR,IR和UV-Vis光谱等进行表征,重点研究了六钼酸根有机亚胺衍生物在乙腈溶液中的紫外光谱。研究结果表明,该类化合物具有典型的分子内电子转移的紫外-可见光谱特征,其特征峰位移Δλ_max与苯胺的苯环取代基的共轭效应指数(σ_R)之间存在良好的线性关系。     

基于遗传算法的非线性映射预测硝基苯化合物的生物毒性

摘要: 非线性映射是一种降维处理技术,通过Sammon算法可以将多维分析问题转化为二维问题分析。应用该法的关键在于寻求二维空间的最佳投影点,这可以转化为一个复杂的非线性优化问题来进行解决。遗传算法是解决各类函数优化和非线性映射问题的一种有效算法。以硝基苯化合物的生物毒性的模式识别为例,编制基于误差函数的目标函数和遗传算法约束参数,应用基于MATLAB的遗传算法工具箱进行优化求解。结果表明:该工具箱在求解此类非线性优化问题上是有效的, 基于遗传算法的非线性映射的预测结果比其它方法要好些。     

基于Beta函数及其偏导数的广义积分的高精度快速计算

考虑Beta函数偏导数的计算以及与此相关的广义积分的高精度快速计算问题.首先将Beta函数B(x,y)的定义扩展到整个复平面上,并建立了在整个复平面上Beta函数B(x,y)的偏导数的递推公式.对许多广义积分我们给出Beta函数偏导数的表示形式,因而利用Beta函数的偏导数计算这些广义积分.数值计算表明,算法无论从计算精度还是计算速度,远好于数值积分.另外,得到了B_(p,q)(x,y)存在闭形式的条件,并给出一些广义积分的闭形式.     

薄膜光学参数表征误差处理技术

针对光度测量数据中难以消除的系统误差对薄膜光学参数表征精度的负面影响,提出一种新型的误差处理技术。选取薄膜光谱系数对折射率和几何厚度的一阶偏导数,对大部分测量入射角满足符号相反或只有其中一个为零的条件的波段,剔除偏导数对全部测量入射角满足符号相同或同时为零条件的奇点波长附近波段,作为反演表征用的光度测量数据采集区域,以最小化光度测量系统误差引起的薄膜光学参数反演表征值相对真实值的偏差大小。通过数值模拟实验,对比研究了该技术对不同偏振光和不同测量入射角范围的适用性及实施技巧,以可复现的数值实验数据和合理的理论解释支持和验证了这种误差处理技术的可靠性。     

Generalized Bessel functions: Theory and their applications

This paper presents 2 new classes of the Bessel functions on a compact domain [0,T] as generalized‐tempered Bessel functions of the first‐ and second‐kind which are denoted by GTBFs‐1 and GTBFs‐2. Two special cases corresponding to the GTBFs‐1 and GTBFs‐2 are considered. We first prove that these functions are as the solutions of 2 linear differential operators and then show that these operators are self‐adjoint on suitable domains. Some interesting properties of these sets of functions such as orthogonality, completeness, fractional derivatives and integrals, recursive relations, asymptotic formulas, and so on are proved in detail. Finally, these functions are performed to approximate some functions and also to solve 3 practical differential equations of fractionalorders.     

High‐order compact schemes for fractional differential equations with mixed derivatives

In this article, we consider two‐dimensional fractional subdiffusion equations with mixed derivatives. A high‐order compact scheme is proposed to solve the problem. We establish a sufficient condition and show that the scheme converges with fourth order in space and second order in time under this condition.© 2017 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 33: 2141–2158, 2017     

Structural and Spectral Study of Nickel(II) Complexes of Pyridyl bis{3‐piperidyl‐, bis{hexamethyleneiminyl‐, bis{N(4)‐diethyl‐, and bis{N(4)‐dipropylthiosemicarbazones}

Pyridyl bis(N(4)‐substituted thiosemicarbazones), in which the substituents replacing the NH₂ group on the thiosemicarbazone moieties are piperidyl, H₂Plpip; hexamethyleneiminyl, H₂Plhexim; diethylamino, H₂Pl4DE; and dipropylamino, H₂Pl4DP, have been synthesized. These bis(thiosemicarbazones) and their nickel(II) complexes have been characterized with IR, electronic, mass, and ¹H and ¹³C NMR spectra. Crystal structures have been solved for H₂Plpip and all four nickel(II) complexes. H₂Plpip does not possess hydrogen bonding between the thiosemicarbazone moieties, but is in the Z isomeric form with intramolecular hydrogen bonding from both thiosemicarbazone moieties to pyridine nitrogen atoms. The nickel(II) complexes possess square‐planar N₂S₂ (i. e., imine nitrogen and thiolato sulfur atoms) centers and the two pyridine ring nitrogen atoms are not coordinated.     

Effects of substituent and solvent on the structure and spectral properties of maleimide derivatives

The maximum absorption wavelength , emission wavelength (λ_em) and the related oscillator strength (f) of the maleimides in the ground and first excited states were calculated by using the DFT, CIS and the time-dependent density functional theory (TD-DFT) methods, where the molecular structures were optimized by DFT/B3LYP/6-31G^* calculation. Solvent effects on the maleimides were examined using the PCM simulation at DFT/B3LYP level with the 6-31G^* basis set. For N-substituted maleimide, the substituent gives only a slight influence on the maleimide chromophore, while planar conformation of PhMLH leads to the improvement in π-delocalization from substituent to maleimide unit. For 3,4-substituted maleimide, the steric repulsion between substituent and maleimide chromophore influences the extent of π-delocalization and the molecular conformation. The calculated and λ_em of maleimides are in good agreement with the experimental data. In the gas phase, both absorption and emission peaks are red-shift as compared to the non-substituted maleimide. Under solvent environment, the more planar conformation of PhMLH shows a blue-shift in the calculated and λ_em as compared with other N-substituted maleimides. For 3,4-substituted maleimides, the effect of substitution produces the most significant spectral red-shift as compared to other maleimides.     

Cyclopalladation of N-phenyl-4-ferrocenylmethylpyrazoles: Crystal structure of [Pd{κ-C,N-C6H4-1-[(3,5-Me2-C3N2)-CH2-(η-C5H4)Fe(η-C5H5)]}Cl(PPh3)] · CH2Cl2

The synthesis and characterization of pyrazole derivatives of general formula [C₆H₄-4-R-1-{(3,5-Me₂-C₃N₂)-CH₂-(η⁵-C₅H₄)Fe(η⁵-C₅H₅)}] [R = OMe (1a) or H (1b)] with a ferrocenylmethyl substituent are described.The study of the reactivity of compounds 1 with palladium(II) acetate has allowed the isolation of complexes (μ-AcO)₂[Pd{κ²-C,N-C₆H₃-4-R-1-[(3,5-Me₂-C₃N₂)-CH₂-(η⁵-C₅H₄)Fe(η⁵-C₅H₅)]}]₂ (2) [R = OMe (2a) or H (2b)] that contain a bidentate [C(sp², phenyl), N]⁻ ligand and a central “Pd(μ-AcO)₂Pd” unit.Furthermore, treatment of 2 with LiCl produced complexes (μ-Cl)₂[Pd{κ²-C,N-C₆H₃-4-R-1-[(3,5-Me₂-C₃N₂)-CH₂-(η⁵-C₅H₄)Fe(η⁵-C₅H₅)]}]₂ (3) [R = OMe (3a) or H (3b)] that arise from the replacement of the acetato ligands by the Cl⁻.Compounds 2 and 3 also react with PPh₃ giving the monomeric complexes [Pd{κ²-C,N-C₆H₃-4-R-1-[(3,5-Me₂-C₃N₂)-CH₂-(η⁵-C₅H₄)Fe(η⁵-C₅H₅)]}X(PPh₃)] {X⁻ = AcO⁻ and R = OMe (5a) or H (5b) or X⁻ = Cl⁻ and R = OMe (6a) or H (6b)}, where the phosphine is in a cis-arrangement to the metallated carbon atom. Treatment of 3 with thallium(I) acetylacetonate produced [Pd{κ²-C,N-C₆H₃-4-R-1-[(3,5-Me₂-C₃N₂)-CH₂-(η⁵-C₅H₄)Fe(η⁵-C₅H₅)]}(acac)] (7) [R = OMe (7a) or H (7b)]. Electrochemical studies of the free ligands and the cyclopalladated complexes are also reported. The dimeric complexes 3 also react with MeO₂C-CC-CO₂Me (in a 1:4 molar ratio) giving [Pd{(MeO₂C-CC-CO₂Me)₂C₆H₃-4-R-1-[(3,5-Me₂-C₃N₂)-CH₂-(η⁵-C₅H₄)Fe(η⁵-C₅H₅)]}Cl] (8) [R = OMe (8a) or H (8b)], which arise from the bis(insertion) of the alkyne into the σ{Pd-C(sp², phenyl)} bond of 3.