Direct assignment of positional isomers by mass spectrometry: ortho,meta and para acyl and amidyl anilines and phenols and derivatives

A direct MS/MS method for the ortho, meta or para configuration assignment of any single molecule that forms reference ions upon ionization and dissociation is demonstrated. Gas-phase structure diagnostic ion–molecule reactions with acetonitrile are shown to distinguish the isomeric 2-, 3- and 4-hydroxybenzoyl cations and the 2- from the 3- and 4-aminobenzoyl cations. These reference ions, which display indistinguishable 15 eV collision-induced dissociation product ion mass spectra, react with acetonitrile to yield characteristic ratios of product ions, most particularly for the 2-isomers. The reactivity of the 2-benzoyl cations is the most characteristic since the ortho configuration allows for [4⁺ + 2] polar cycloaddition that yields relatively stable heterocycles in N-protonated forms. Distinction of the reference isomeric 2-, 3- and 4-hydroxy- and aminobenzoyl cations permits, therefore, partially or completely, direct ‘MS-only’ positional assignment of either ortho, meta or para configuration for any single molecule that forms such reference ions upon ionization and dissociation. This “class-universal” method for direct MS assignment of a single positional isomer should therefore be applicable to many members of the homologous series of isomeric ortho, meta and para acyl and amidyl anilines and phenols and derivatives. Such molecules dissociate, or are likely to dissociate, after or during ionization processes to form the reference and structurally diagnostic ortho, meta or para hydroxy- or aminobenzoyl cations. Copyright © 2004 John Wiley & Sons, Ltd.     

Investigations on temperature dependent structural evolution of NaPO3 glass

The understanding of molecular level structural information of phosphate glasses is very much essential. The unique microwave-absorbing ability of NaH₂PO₄·2H₂O was found to be very useful for preparing crystal and glassy sodium super ionic conductors (Nasicon's) as a component of batch mixtures. In this work NaPO₃ glass was prepared by both conventional melt quench and microwave heating from NaH₂PO₄·2H₂O as a starting material. The structure of NaPO₃ glass and their structural evolution upon heating through glass transition were probed by combination of complementary techniques like differential scanning calorimetry (DSC), powder X-ray diffraction (PXRD), Fourier transform infrared (FT-IR) and thermo-Raman spectroscopy.This revised version was published online in November 2005 with corrections to the Cover Date.     

IM－DD SCM光波系统的非线性分析

本文在简要分析了激光器非线性机理的基础上,采用计算机模拟及数学归纳的方法,着重分析了IM-DDSCM光纤通信系统中各种非线性失真项的数目、幅度及其抑制方法,归纳出了落入各个信道中的各种非线性失真项的数目的数学表达式,推导出了非线性失真项的功率之和的计算公式;通过对计算结果的比较得知,激光器P-I曲线的非线性是影响系统非线性失真的主要因素,指出了利用预失真的方法补偿激光器P-I曲线非线性的影响。     

(Al)GaAs/AlGaAs周期光波导中的等幅基模

本文应用周期介质光波导的模场分布函数和特征方程分析了(Al)GaAs/AlGaAs周期光波导中结构参量及介质折射率对模场分布形状的影响,研究了波导中形成等幅基模的条件,讨论了相应参量的优化选择。     

硅酸锶掺Eu^3^＋的高压合成及发光特性

首次采用高压高温方法合成了Sr_2SiO_4:Eu~(3+)Bi~(3+)和SrSiO_3:Eu~(3+)Bi~(3+)发光材料,研究了合成压力、合成温度对发光特性的影响。与常压合成产物相比较,发光谱线发生了红移;谱线半宽度显著增大;发光强度和量子发光效率下降。X射线衍射分析得出,SrSiO_3:Eu~(3+)Bi~(3+)发生了结构相变,Sr_2SiO_4:Eu~(3+)Bi~(3+)结构未变但晶格参数发生了变化,且主衍射峰强度发生了反转。分析表明,发光特性的变化是压致晶场、库仑及自旋～轨道相互作用的变化引起的。     

层状结构簇合物FeNb_2Te_4和Fe_2Nb_2Te_4的穆斯堡尔谱和晶体结构研究

测定了FeNb_2Te_4和Fe_2Nb_2Te_4的穆斯堡尔谱和晶体结构。它们的穆斯堡尔谱都是一组对称的四极分裂双峰。实验数据用最小二乘法计算机程序拟合。经计算机拟合后的穆斯堡尔参数(在77K时)为:对于FeNb_2Te_4,δ=0.409±0.004 mm/s,△F_Q=0.633±0.004 mm/s,线宽r=0.372±0.004 mm/s;对于Fe_2Nb_2Te_4,δ=0.425±0.004mm/s,△E_Q=0.671±0.004mm/s,r=0.404±0.004 mm/s。化学位移δ值是相对于α-Fe的。由X衍射单晶结构测定得出,FeNb_2Te_4属正交晶系,空间群Pmmn,晶胞参数:a=1.2432(4)nm,b=0.3796(1)nm,c=0.7314(4)nm,V=0.3452(4)nm~3,Z=2。Fe_2Nb_2Te_4也是属正交晶系,空间群Pma2,晶胞参数:a=0.7955(1)nm,b=0.6258(1)nm,c=0.7202(2)nm,V=0.3585(3)nm~3,Z=2。从穆斯堡尔参数可确定这两个簇合物的Fe原子都属高自旋+3价,而且都处在晶格中的等价位置,这与单晶结构测定的结果相一致。     

Microstructures and Optical Properties of Scales of Butterfly Wings

This paper describes the mechanism generating the beautiful wing colors of various male butterflies and the relationship between the wing material and the color appearance. The microstructure of the scales covering the upper surface of the wings was analyzed with the aid of a scanning electron microscope. The basic mechanism of color generation of structurally colored scales is determined for the first time in accordance with the theory of optical interference in thin film layers using a model of wing scales. Optical properties were found in relation to the three-dimensional spectral reflectance of the samples, and differences were observed between the brightness perceived in subjective evaluations and calculated values based on the reflective spectra of the structurally colored wings. The results of this study suggest that the microroughness of the upper wing surface may influence the perceived gloss of structurally colored wings.     

菱面片层氧化镁的制备及晶格畸变与反常红外特性

以低品位白云石为原料采用二次酸浸、EDTA-氨水沉淀法制备前驱体Mg（OH）2，经煅烧得到菱面片层状多空隙结构的纳米MgO晶体。通过X射线衍射（XRD）、高分辨率扫描电镜（HRSEM）及傅立叶红外光谱（FT—IR）等测试手段对所得产物的物相和形貌等进行了表征。分析表明：氧化镁为结晶良好、立方晶系，厚度约10～20nm，最大面积可达1μm^2左右的菱形纳米片层结构；XRD数据表明纳米氧化镁的微结构存在晶格畸变并导致XRD相位差发生变化；红外光谱表明，Mg-O键伸缩特征吸收峰向高波数方向移动（蓝移）了约84．82cm^-1，而弯曲特征吸收峰向低波数方向移动（红移）了约31．88cm^-1，并导致红外吸收光谱的宽频化。结合XRD数据分析结果和界面效应等物理现象讨论了反常红外吸收机理。