摘要
蒽醌化合物是重要的染料和医药中间体，由于应用广泛，在生产和消耗过程中难免会进入环境中。光解是有机物在环境中的重要归趋之一，因此有必要研究蒽醌化合物的光解行为。
本研究以高压汞灯为光源，测定了15种蒽醌化合物的光解速率常数(k)，讨论了化学结构(取代基位置、数目及种类)、溶剂(二甲基亚砜、二甲基亚砜+水)对其光解速率的影响。选取9种氨基蒽醌，应用偏最小二乘算法(PLS)，建立了光解速率常数的定量结构-性质关系模型(QSPR)，得出影响这些氨基蒽醌光解速率的主要因素是：分子生成热、氢原子所带最大正电荷、碳原子所带最大负电荷，此外分子最低未占据轨道与最高占据轨道的能量差对这些氨基蒽醌的光解也有一定影响。
以1-氨基-4-羟基蒽醌为研究对象，比较了不同类型溶剂对其光解速率的影响，发现极性非质子型溶剂可以加快其光解。光敏性是蒽醌化合物的重要性质之一，间接法检测表明，光照条件下1-氨基-4-羟基蒽醌能产生超氧负离子自由基(O_2~(·-))和单线态氧(~1O_2)，同时考察了1-氨基-4-羟基蒽醌的光解动力学，得出其光解反应中直接光解占43.0％，间接光解占57.0％，其中~1O_2和O_2~(·-)的贡献分别为26.1％和30.9％。前线电子密度法预测并通过GC／MS分析验证，得到1-氨基-4-羟基蒽醌光解产物主要为1，4-二羟基蒽醌。结合理论分析、实验结果及前人研究，提出了三种可能的1-氨基-4-羟基蒽醌光解途径：直接光解途径，受到~1O_2攻击的反应途径和受到O_2~(·-)攻击的反应途径；推测1-氨基-4-羟基蒽醌产生光致毒性的原因可能是光敏化作用；1-氨基-4-羟基蒽醌光解生成1，4-二羟基蒽醌是一种对环境有利的转化。
Anthraquinones are a group of important intermediate of dye and medicament. Because of widely applying, they would enter into the environment during producing and consuming. Note that the photolysis is one of important transformations of these chemicals in the environment, it is necessary to investigate the photolysis of anthraquinones.
The study determined the photolysis rate constants of 15 anthraquinones irradiated by high-pressure mercury lamp and discussed the effects of the position, number and species of substituted group on photolysis rates. Also, the effect of solvents, dimethyl sulfoxide (DMSO) and DMSO containing water, on photolysis rate was investigated. To study the photolysis mechanism of the anthraquinones, 9 aminoanthraquinones were selected to establish the quantity structure-properties relationship (QSPR) using partial least square (PLS). The results indicated that the factors affecting the photolysis rate were the heat of formation, the most positive net atomic charges on a hydrogen atom, the largest negative atomic charge on a carbon atom, and the energy gap between the lowest unoccupied molecular orbital and the highest occupied molecular orbital.
On the other hand, the effect of solvents on the photolysis of 1-amino-4-hydroxyanthraquinone was discussed and it can be concluded that the polarity and nonprotonic solvent can accelerate the photolysis rate. Under the condition of light irradiation, 1-amino-4-hydroxyanthraquinone can generate O_2~(·-) and ~1O_2. In the course of its photolysis, direct photolysis and indirect photolysis occupied 43.0% and 57.0% respectively. In view of indirect photolysis, ~1O_2 and O_2~(·-) contributed 26.1% and 30.9% respectively. The results obtained from the frontier electron density calculation and GC/MS further proved that 1,4-dihydroxyanthraquinone was the primary photoproduct of 1-amino-4-hydroxyanthraquinone. Based on the currently experimental results, theoretical analysis and availably previous studies, three pathways of 1-amino-4-hydroxyanthraquinone photodegradation were proposed: direct photolysis pathway, ~1O_2 attack pathway and O_2~(·-) attack pathway. It confirmed that the photoinduced toxicity of 1-amino-4-hydroxyanthraquinone maybe induced by photosensitization mechanism. Moreover, the phototransformation from 1-amino-4-hydroxyanthraquinone to 1,4-dihydroxyanthraquinone was a process of environmentally acceptable.
引文
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