Self-quenching in the electrochemiluminescence of tris(2,2'-bipyridyl) ruthenium(ii) using metabolites of catecholamines as co-reactants

Electrochemiluminescence (ECL) of Ru(bpy)(3)(2+) using metabolites of catecholamines: homovanillic acid (HVA) and vanillylmandelic acid (VMA) as co-reactants were investigated in aqueous solution for the first time. When HVA and VMA were co-existent in the buffer solution containing Ru(bpy)(3)(2+), ECL peaks were observed at a potential corresponding to the oxidation of Ru(bpy)(3)(2+), and the ECL intensity was increased noticeably when the concentrations of HVA and VMA were at lower levels. The linear calibration range was from 8.0 × 10(-5) to 1.0 × 10(-9) M for HVA and VMA. The detection limit (S/N = 3) of HVA and VMA was 4.0 × 10(-10) M. The formation of the excited state Ru(bpy)(3)(2+*) was confirmed to result from the reaction between Ru(bpy)(3)(3+) and the intermediates of HVA or VMA radicals. Moreover, it was found that the ECL intensity was quenched significantly when the concentrations of HVA and VMA were relatively higher. The mechanism of self-quenching processes involved in the Ru(bpy)(3)(2+)-HVA and -VMA ECL systems are proposed in this study.     

Measuring the subprime crisis contagion: Evidence of change point analysis of copula functions

In this paper, we first determine the existence of structural changes in the dependence between time series of equity index returns of two markets using the change point testing method. The method is based on Archimedean copula functions, which are able to comprehensively describe dependence characteristics of random variables. The degree of financial contagion between markets is subsequently estimated using the tail dependence coefficient of copula functions before and after the change point. We empirically test our method by investigating financial contagion during the subprime crisis between the US S&P 500 index and five Asian markets, namely China, Japan, Korea, Hong Kong and Taiwan. Our results show that a statistically significant change point exists in the dependence between the US market and all Asian stock markets except Taiwan. The upper tail dependence is larger after the time of change, implying the existence of contagion during the banking crisis between the US and the Asian economies. The degree of financial contagion is also estimated and found to be consistent with market events and media reports during that period.     

缝合复合材料制备工艺和力学性能研究

从缝合复合材料的工程实际应用、工艺、力学性能、分析方法等方面对缝合复合材料的制备工艺和力学性能研究发展状况进行了比较全面系统的阐述与分析,重点介绍了缝合复合材料的各种力学性能及其强度分析模型.在强度分析模型中, 介绍了弹性矩阵场函数和缝合复合材料强度场的概念.缝合复合材料在结构整体性、层间性能以及低速冲击损伤阻抗等方面具有明显的优势,克服了普通层合板层间性能以及低速冲击后压缩性能低的弱点. 但是,缝合复合材料的工艺相对比较复杂,缝合对层合板的部分面内力学性能存在一定的负面影响,而且在湿热环境条件下其层间强度高的优势无法发挥.在选用缝合时,应根据所用层合板的铺层顺序及其使用的环境条件,同时还应兼顾缝合对铺层面内力学性能的影响, 决定是否使用缝合结构.在湿热性能要求不高的结构中, 如导弹结构,缝合复合材料已经得到了很好的应用.      

巯基钴卟啉自组装膜的表征及催化性能

用自制的新型尾式巯基钴（Ⅱ）卟啉在金电极上制成自组装单分子膜,并用ＸＰＳ,ＳＥＭ和电化学的方法进行了表征。该膜对抗坏血酸具有良好的催化作用,其氧化过电位较裸金电极上降低了１４０ ｍＶ,响应电流与抗坏血酸（ＡＡ）的浓度在 ７．８ × １０－５ｍｏｌ／Ｌ～１．０×１０－２ｍｏｌ／Ｌ的范围内具有良好的线性关系,相关系数为 ０．９９８１;检测下限为 １．３ × １０－８ｍｏｌ／Ｌ（富集 １０ｍｉｎ）。     

三元混配络合物形成的极谱研究——Cd-Bipy-Gly体系的稳定常数测定

用般谱法研究了Cd(Ⅱ)-2,2′-联吡啶(bipy)、Cd(Ⅱ)-甘氨酸(Gly)二元体系及cd(Ⅱ)-bipy-Gly三元体系的配合物的形成条件,用极谱法测定了不同浓庹配体的E_1/2(a)、E_1/2(c)、ΔE_1/2、(i_d)_s和(i_d)_c值,利用Lrden函数作图,外推求得各级稳定常数。     

伏安法中离散数据的傅里叶最小二乘处理方法

提出了傅里叶最小二乘法对含噪声伏安数据的处理，并讨论其原理。通过对理论模拟数据和甲醛实验体系中高噪声溶出伏安数据的处理，证明了Ｆｏｕｒｉｅｒ最小二乘法的可行性。     

分析化学计量学中的新方法─—小波分析

小波分析在分析信号处理中具有诸多显著的优点。本文介绍了小波分析的一般描述，综述了化学计量学在的小波新方法，并展望了小波分析在分析化学计量学中的应用前景。     

Synthesis and Characterization of Three New Unsymmetrical Porphyrins

The synthesis and characterization of three new unsymmetrical porphyrins is reported. These porphyrins are isomers and have not been reported previously. A new method was used to synthesize the porphyrins which is different from the general synthetic porcedure which was developed by Adler ^[1]. The structural assignment of the three isomers was based on the elemental analyses, UV-Vis, IR, and ¹HNMR spectra.     

The photophysics of the 2,6 dialkoxy anthracenes: Evidence for excited state side-chain conformational relaxation

Three 2,6 dialkoxyanthracenes with varying ether sidechain lengths (methyl, n-propyl and n-hexyl) are synthesized and characterized. When compared to unsubstituted anthracene, the spectroscopic properties of the alkoxy-anthracenes are significantly different. The oscillator strength appears to be evenly distributed between the L_a and L_b states, rather than concentrated in the low-energy L_a state, and the transition dipole moments are rotated by ～30° in the molecular frame. More importantly, all three derivatives undergo an intramolecular conformational change in the excited state that gives rise to a reshaping of the fluorescence spectrum on the nanosecond timescale. This process has an activation energy of 8±1 kJ/mol. By ～150 K the fluorescence spectrum reflects only the high energy conformer, whose emission lineshape is similar to that of the unsubstituted anthracene. The temperature-dependent changes in the monomeric fluorescence spectra of these compounds will have to be taken into account in future studies of their solid-state spectroscopy.