期刊
SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY
卷 185, 期 -, 页码 104-110出版社
PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.saa.2017.05.040
关键词
Electronic absorption spectroscopy; Quantum chemical calculation; Multivariate analysis; Chemometrics; Bromthymol blue; Structural analysis
类别
资金
- JSPS KAKENHI [JP26810001, JP16K13619, JP15H02185]
- Collaborative Research Program of Institute for Chemical Research, Kyoto University [2015-85, 2016-75]
- Grants-in-Aid for Scientific Research [16K13619] Funding Source: KAKEN
The pH dependent chemical structures of bromothymol blue (BTB), which have long been under controversy, are determined by employing a combined technique of multivariate analysis of electronic absorption spectra and quantum chemistry. Principle component analysis (PCA) of the pH dependent spectra apparently reveals that only two chemical species are adequate to fully account for the color changes, with which the spectral decomposition is readily performed by using augmented alternative least-squares (ALS) regression analysis. The quantity variation by the ALS analysis also reveals the practical acid dissociation constant, pK(a)'. The determination of pKa' is performed for various ionic strengths, which reveals the thermodynamic acid constant (pK(a) = 7.5) and the number of charge on each chemical species; the yellow form is negatively charged species of 1 and the blue form that of -2. On this chemical information, the quantum chemical calculation is carried out to find that BTB molecules take the pure quinoid form in an acid solution and the quinoid-phenolate form in an alkaline solution. The time-dependent density functional theory (TD-DFT) calculations for the theoretically determined chemical structures account for the peak shift of the electronic spectra. In this manner, the structures of all the chemical species appeared in equilibrium have finally been confirmed. (C) 2017 Elsevier B.V. All rights reserved.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据