Use of evolutionary factor analysis in the spectroelectrochemistry of Escherichia coli sulfite reductase hemoprotein and a Mo/Fe/S cluster.
Use of evolutionary factor analysis in the spectroelectrochemistry of Escherichia coli sulfite reductase hemoprotein and a Mo/Fe/S cluster.
复制标题
进化因子分析在大肠杆菌亚硫酸还原酶血红蛋白和 Mo/Fe/S 簇的光谱电化学中的应用。
DOI：
10.1021/ac981079h
复制
发表时间：
1999
影响因子：
7.4
通讯作者：
Ryan,MD
中科院分区：
文献类型：
--
作者：
Keesey,RL;Ryan,MD
如果中间产物的光谱不知道，光谱电化学数据的反褶积往往是相当困难的。然而，因子分析已被证明是一种强大的技术，可以使重叠光谱的反卷积成为可能。在这项工作中，进化因子分析将用于确定两种典型的光谱电化学实验的中间体数量和这些物种的光谱：线性扫描伏安法和薄层电池的时间吸收法。第一个系统是e的减少。粘性亚硫酸盐还原酶血红蛋白（SiR-HP）。主因子分析表明有3种。通过进化因子分析，确定了每种物质存在的潜在区域，并利用质量平衡方程确定了它们的浓度和光谱。对单电子还原产物（SiR-HP1-）和双电子还原产物（SiR-HP2-）的光谱进行了比较。第二个实验是二氯甲烷中cl2fes2mos2fec22的时间吸收法。实验结果表明，实验过程中存在五种物种。假设电解过程中有4种物质存在，对61个光谱进行拟合。后来物种出现的速率常数与以前物种消失的速率常数非常吻合。利用演化因子分析和质量平衡方程得到了中间体和最终产物的光谱。第五种可能是初始还原产物Cl2FeS2MoS2FeCl23-，由于其浓度低且与起始物质存在于同一时间区域，因此鉴定困难。
The deconvolution of spectroelectrochemical data is often quite difficult if the spectra of intermediates are not known. Factor analysis, however, has been shown to be a powerful technique which can make it possible to deconvolute overlapping spectra. In this work, evolving factor analysis will be used to determine the number of intermediates and the spectra of those species for two typical spectroelectrochemical experiments: linear scan voltammetry and chronoabsorptometry in a thin-layer cell. The first system was the reduction ofE.colisulfite reductase hemoprotein (SiR-HP). Principal factor analysis indicated that three species were present. By using evolving factor analysis, the potential regions where each of the species were present were identified, and their concentrations and spectra were determined by the use of the mass balance equation. The spectra of the one-electron (SiR-HP1-) and two-electron (SiR-HP2-) reduced product were compared with previous work. The second experiment was the chronoabsorptometry of Cl2FeS2MoS2FeCl22-in methylene chloride. This experiment indicated that five species were present during the experiment. The entire set of 61 spectra were fit by assuming that there were 4 species present during the electrolysis. The rate constant for the appearance of subsequent species fit quite well with the rate constant for the disappearance of previous species. The spectra of the intermediates and final product were obtained using evolving factor analysis and a mass balance equation. Identification of the fifth species, which was probably the initial reduction product, Cl2FeS2MoS2FeCl23-, was difficult due to its low concentration and the fact that it was present in the same time region as the starting material.