2,5-二甲氧基-4-氯硝基苯与硫化钠的反应

硫化钠和二硫化钠分别在95%乙醇中与2,5-二甲氧基-4-氯硝基苯反应, 原本期望得到2,5-二甲氧基-4-氯苯胺, 然而对产物结构的1H NMR, 13C NMR, MS以及元素分析结果表明, 2,5-二甲氧基-4-氯硝基苯中的硝基没有被硫化钠和二硫化钠还原成氨基, 而是其中的氯原子被硫离子(或二硫离子)取代, 分别生成了4,4’-硫代-2,2’,5,5’-四甲氧基-双硝基苯和4,4’-双硫代-2,2’,5,5’-四甲氧基-双硝基苯. 根据这个实验事实, 讨论了上述亲核取代反应的机理.     

A porphyrin derivative containing 2-(oxymethyl)pyridine units showing unexpected ratiometric fluorescent recognition of Zn2+ with high selectivity

A porphyrin derivative (1), containing two 2-(oxymethyl)pyridine units has been designed and synthesized as chemosensor for recognition of metal ions. Unlike many common porphyrin derivatives that show response to different heavy metal ions, compound 1 exhibits unexpected ratiometric fluorescence response to Zn²⁺ with high selectivity. The response of the novel chemosensor to zinc was based on the porphyrin metallation with cooperating effect of 2-(oxymethyl)pyridine units. The change of fluorescence of 1 was attributed to the formation of an inclusion complex between porphyrin ring and Zn²⁺ by 1:1 complex ratio (K = 1.04 × 10⁵), which has been utilized as the basis of the fabrication of the Zn²⁺-sensitive fluorescent chemosensor. The analytical performance characteristics of the proposed Zn²⁺-sensitive chemosensor were investigated. The sensor can be applied to the quantification of Zn²⁺ with a linear range covering from 3.2 × 10⁻⁷ to 1.8 × 10⁻⁴ M and a detection limit of 5.5 × 10⁻⁸ M. The experiment results show that the response behavior of 1 to Zn²⁺ is pH-independent in medium condition (pH 4.0-8.0) and show excellent selectivity for Zn²⁺ over transition metal cations.     

Study on the absorption and fluorescence and resonance Rayleigh scattering spectra of Cu (II)-fluoroquinolone chelates with erythrosine and their applications

In pH 4.2-5.0 Britton-Robinson buffer solution medium, fluoroquinolone antibiotics (FLQs), such as ciprofloxacin (CIP), norfloxacin (NOR), ofloxacin (OF), levofloxacin (LEV), lomefloxacin (LOM), and sparfloxacin (SPA), react with Cu (II) to form chelate cations, which further bind with erythrosine to form the ion association complexes. They can result in the changes of the absorption spectra. Simultane- ously, erythrosine fades obviously and the maximum fading wavelength is located at 526 nm. The fad- ing reactions have high sensitivities. Thus, new spectrophotometries of determination for these drugs are developed. The ion-association reactions result in the quenching of fluorescence, which also have high sensitivities. The detection limits for six antibiotics are in the range of 7.1-12.2 μg·L?1. Furthermore, the reactions can result in the enhancement of resonance Rayleigh scattering (RRS). The maximum scattering peaks of six ion-association complexes are located at 566 nm, and there are two small RRS peaks at 333 nm and 287 nm. The detection limits for fluoroquinolone antibiotics are in the range of 1.70 -3.10 μg·L?1 for RRS method. Among the above three methods, the RRS method has the highest sen- sitivity. In this work, we investigated the spectral characteristics of the absorption, fluorescence and RRS, the optimum conditions of the reactions, and the properties of the analytical chemistry. In addi- tion, the mechanism of reactions were discussed by density function theory (DFT) and AM1 methods.     

Nb∶KTiOPO4晶体的生长和倍频性能

通过研究晶体生长工艺参数对Nb∶KTiOPO4(Nb∶KTP)晶体生长的影响,用熔盐顶部籽晶法获得尺寸为55mm×25mm×5mm的Nb∶KTP透明单晶.研究中发现熔体的温度梯度、籽晶和降温速率将严重影响Nb∶KTP晶体的生长.Nb离子的引入不利于Nb∶KTP晶体的生长,尤其是造成晶体易开裂,且沿a轴方向生长速度非常缓慢.同时,Nb的引入大大改变Nb∶KTP晶体的倍频性能.掺杂Nb浓度的摩尔分数为13;时,Nb∶KTP晶体的倍频的Ⅱ型相位匹配的截止波长缩短至937nm,且有效产生469nm倍频蓝光;掺杂Nb浓度的摩尔分数为3;时,Nb∶KTP晶体对Nd∶YAG的1.0642μm激光倍频的最佳相位匹配角为θ=88.32°,()=0°,非常接近90°非临界相位匹配方向.     

FUNDAMENTALS OF TRANSMISSION FLUCTUATION SPECTROMETRY WITH VARIABLE SPATIAL AVERAGING

Transmission signal of radiation in suspension of particles performed with a high spatial and temporal resolution shows significant fluctuations,which are related to the physical properties of the particles and the process of spatial and temporal averaging.Exploiting this connection,it is possible to calculate the particle size distribution (PSD) and particle concentration.This paper provides an approach of transmission fluctuation spectrometry (TFS) with variable spatial averaging,The transmission fluctuations are expressed in terms of the expectancy of transmission square (ETS) and are obtained as a spectrum,which is a function of the variable beam diameter.The reversal point and the depth of the spectrum contain the information of particle size and particle concentration,respectively.     

A SIMPLIFIED CALCULATING METHOD OF NONLINEAR FREQUENCY OF CABLE NET UNDER MEAN WIND LOAD

The cable net supported glass curtain wallas the most advanced technique in dot point supported glass curtain wall, is widely used in China. Because of its large deflection and high nonlinearity under wind load, the dynamic performance of the cable net is greatly different from that of the conventional linear structures. The continuous membrane theory is used to construct the nonlinear vibration differential equation of the cable net, and the harmonic balance method is used to solve the analytic formula of the nonlinear frequency. In order to verify the accuracy of the above analytic formula, the results of the formula and the nonlinear FEM time-history method are compared and found to be in good agreement. Furthermore, the nonlinear vibration differential equation and the nonlinear frequency obtained in this paper are the basis for the wind-induced response analysis of a cable net under fluctuating wind load.     

接地式三要素型动力吸振器性能分析

利用固定点理论优化接地类型的动力吸振器得到的结果可能不是全局最优参数,在选择其他参数时主系统可以获得更小的振幅, 接地类型动力吸振器的优化问题值得进一步研究. 因此,以一种接地式三要素型动力吸振器为对象,通过研究系统参数变化对固 定点位置与主系统最大振幅的影响,得到了此吸振器的局部最优参数并分析了它的性能. 首先建立了此系统模型的运动微分方程, 得到了主系统振幅放大因子,发现系统存在3个与阻尼无关的固定点. 固定点中幅值较大点随系统参数变化的趋势可以代表最大振 幅随系统参数变化的趋势,因此利用盛金公式得到了固定点幅值的表达式. 为了更加精确,进一步使用数值算法得到了最大振幅与 系统参数的关系图,发现系统中存在局部最优参数. 通过对比接地式吸振器与接地三要素型吸振器的最大振幅随系统参数变化的趋 势,得到了接地式三要素型吸振器的局部最优参数,并发现当固有频率比小于局部最优频率比时,接地式三要素型吸振器模型主系 统的最大振幅要远小于接地式动力吸振器模型.      

光纤传感器和压电作动片对薄板振动控制的分析

利用双模模态域光纤传感器的模间干涉感知薄板结构中应变的变化、获得薄板结构振动变化状况，进一步利用压电体作为动元件，减小振幅，实现振动的主动控制，采用振型叠加法和直接积分相结合的方法，从理论上论证薄板分别受到正弦波激振力，脉冲激振力和方波激振力时的振动主动控制，并由脉冲激振下的响应得到控制前后的幅频特性曲线和相频特性曲线．。