Zavalishin Maksim N, Kiselev Aleksei N, Gamov George A
Department of General Chemical Technology, Ivanovo State University of Chemistry and Technology, Sheremetevskii Pr. 7, Ivanovo 153000, Russia.
G.A. Krestov Institute of Solution Chemistry, Russian Academy of Science, Akademicheskaya Str. 1, Ivanovo 153045, Russia.
Molecules. 2024 Jul 26;29(15):3504. doi: 10.3390/molecules29153504.
Schiff bases are compounds that are widely distributed in nature and have practical value for industry and biomedicine. Another important use of Schiff bases is identifying metal ions and different molecules, including proteins. Their proneness to hydrolysis limits the utilization of Schiff bases to mainly non-aqueous solutions. However, by introducing -OH and -SH substituents to aromatic amine-bearing rings, it is possible to increase the resilience of the Schiff base to destruction in water. The present paper discusses how the hydroxyl or thiol group influences the spectral properties and kinetics of the hydrolysis and formation of Schiff bases derived from pyridoxal 5'-phosphate and aniline, 2-hydroxyaniline, and 2-mercaptoaniline using quantum chemical data. The spectral variation between different imines can be explained by taking into account the geometry and frontier molecular orbital alteration induced by the substituents. The changes in the hydrolysis rate are analyzed using the computed values of local reactivity indices.
席夫碱是一类在自然界中广泛分布的化合物，在工业和生物医学领域具有实用价值。席夫碱的另一个重要用途是识别金属离子和不同分子，包括蛋白质。它们易于水解的特性限制了席夫碱主要在非水溶液中的应用。然而，通过在含芳胺的环上引入 -OH 和 -SH 取代基，可以提高席夫碱在水中抗破坏的能力。本文利用量子化学数据讨论了羟基或巯基如何影响由磷酸吡哆醛与苯胺、2-羟基苯胺和2-巯基苯胺衍生的席夫碱的光谱性质以及水解和形成的动力学。不同亚胺之间的光谱变化可以通过考虑取代基引起的几何结构和前沿分子轨道变化来解释。利用计算得到的局部反应性指数分析水解速率的变化。
