Protonation of Patented Blue V in aqueous solutions: theoretical and experimental studies
Protonation of Patented Blue V in aqueous solutions: theoretical and experimental studies
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专利 Blue V 在水溶液中的质子化：理论和实验研究
DOI：
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发表时间：
2018
期刊：
影响因子：
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通讯作者：
D. Snigur
中科院分区：
文献类型：
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作者：
K. Bevziuk;A. Chebotarev;M. Fizer;A. Klochkova;K. Pliuta;D. Snigur
通过分光光度法和三刺激比色法研究了专利 Blue V 染料的酸碱特性。采用半经验和 DFT 方法研究了专利 Blue V 的质子化机理。总能量的量子化学计算定义了水溶液中每种质子化形式最稳定的异构体。除了热力学参数之外，凝聚福井函数和分子静电势也成功地用作反应性描述符，用于确定最有利的质子化位点。此外，为了解释高碱性介质中染料最去质子化形式的结构，用降低的密度梯度函数研究了弱分子内相互作用。吸收光谱的半经验计算解释了不同质子化状态下染料颜色的变化。研究表明，专利 Blue V 的主要形式是电中性形式，摩尔吸光系数 ($$\upvarepsilon _{639}=1.06\times 10^{5}\,\hbox {dm}^{3}\cdot \hbox {mol}^{-1}\cdot \hbox {cm}^{-1})$$ε639=1.06×105dm3·mol-1·cm-1)随着溶剂介电常数的增加而增加。用极性较小的溶剂替代极性溶剂会导致染料吸收带发生红移，其值与汉森参数的值相关。图形摘要概要通过分光光度法和三刺激比色法研究了专利蓝 V 染料的酸碱性质。采用半经验和 DFT 方法研究了专利 Blue V 的质子化机理。确定了染料官能团的电离常数并提出了最可能的质子化/去质子化方案。
The acid-base properties of the Patented Blue V dye were studied by spectrophotometry and tristimulus colourimetry. The mechanism of protonation of Patented Blue V has been investigated with semi-empirical and DFT methods. The quantum chemical calculations of total energy defined the most stable isomer for each protonated form in water solution. In addition to thermodynamic parameters, the condensed Fukui function and molecular electrostatic potential were successfully used as reactivity descriptors for the determination of the most favorable site for protonation. Moreover, for the explanation of the structure of the most deprotonated form of the dye in highly basic medium, the weak intramolecular interactions were investigated with the reduced density gradient function. The semi-empirical calculations of absorbance spectra explained the changing of the colour of the dye for the different protonated states. It has been shown that the dominant form of the Patented Blue V was the electro-neutral form, and the molar absorptivity ($$\upvarepsilon _{639}=1.06\times 10^{5}\,\hbox {dm}^{3}\cdot \hbox {mol}^{-1}\cdot \hbox {cm}^{-1})$$ε639=1.06×105dm3·mol-1·cm-1) increases with the increase of the dielectric permittivity of the solvent. The replacement of polar solvents by less polar ones is causing a bathochromic shift of the absorption band of the dye, the value of which is correlated with the value of the Hansen parameter.Graphical Abstract SYNOPSIS The acid-base properties of the Patented blue V dye were studied by spectrophotometry and tristimulus colourimetry. The mechanism of protonation of Patented Blue V has been investigated with semi-empirical and DFT methods. The ionization constants of the dye functional groups were determined and the most probable protonation/deprotonation scheme was proposed.
影响因子：
15
作者：
Johnson ER;Keinan S;Mori-Sánchez P;Contreras-García J;Cohen AJ;Yang W
通讯作者：
Yang W