研究报告
徐佳禛,牟永晓,曹建平,王朝杰.溴化咪唑类离子液体对胞嘧啶结构和性质影响的计算研究[J].环境科学学报,2018,38(10):4113-4123
溴化咪唑类离子液体对胞嘧啶结构和性质影响的计算研究
- A density functional theory study on effects of imidazolium bromide ionic liquids on the structure and properties of cytosine
- 基金项目：国家自然科学基金（No.21177098）；浙江省自然科学基金（No.LY16B07006）
- 作者
- 单位
- 徐佳禛
- 温州医科大学药学院, 温州 325035
- 牟永晓
- 温州医科大学药学院, 温州 325035
- 曹建平
- 温州医科大学药学院, 温州 325035
- 王朝杰
- 温州医科大学药学院, 温州 325035
- 摘要：离子液体被称为绿色溶剂得到广泛的应用，但离子液体并非完全无毒性，其中关于离子液体基因毒性的相关实验报道不少.本文运用密度泛函理论M06-2X和ωB97XD方法在6-311++G（2d，p）基组水平，对阳离子（C2/4mim+）、阴离子（Br-）、离子液体（[C2/4mim]Br）与胞嘧啶（C）作用体系的几何结构、能量学特征、谱学性质和电子结构等进行计算研究.两种方法计算得到5种最稳定结构C-C2mim-1、C-C4mim-1、C-Br-1、C21和C41，经BSSE校正后的结合能分别为-99.1（-103.9）、-99.6（-104.3）、-102.2（-99.3）、-97.3（-100.7）和-104.5（-105.6）kJ· mol-1，体系中胞嘧啶变形能在2.8~6.9 kJ· mol-1范围内.复合物中胞嘧啶的C2O7和N1-H键的伸缩振动频率均发生一定程度的红移.分子中的原子理论（Atoms in molecule）得到阳离子、阴离子、离子液体与胞嘧啶作用以静电作用为主.自然键轨道分析（Natural bond orbitals）表明C21和C41的稳定化能主要来源于LP Br→BD*N1-H、LP Br→BD*N1-C2和LP O7→BD*C2-H之间的相互作用.极化连续介质模型（Polarizable continum model）计算表明水溶液环境可削弱溴化咪唑类离子液体对胞嘧啶结构和性质的影响.
- Abstract：Ionic liquids are considered as green solvents and thus have been widely used. However, ionic liquids are not completely nontoxic according to a few reports of their genotoxicities. The geometric and electronic structures, energetics, and spectroscopy of[C-C2/4mim+],[C-Br-] and[C-[C2/4mim]Br] were investigated in detail, using the M06-2X and ωB97XD methods with 6-311++G(2d, p) basis set. The five most stable structures C-C2mim-1, C-C4mim-1, C-Br-1, C21 and C41 were obtained at two levels. The BSSE-corrected binding energies of the most stable complexes are -99.1(-103.9), -99.6(-104.3), -102.2(-99.3), -97.3(-100.7) and -104.5(-105.6) kJ·mol-1. In the complexes, the stretching vibrational frequencies of C2O7 and N1-H bonds in cytosine all exhibited a general red-shift. Atoms in molecule analysis indicated that the cations, anion and ionic liquids were mainly an electrostatic interaction with cytosine. Natural bond orbitals analysis showed that the cytosine and[C2/4mim]Br can form considerably strong interaction, which is mainly attributed to the interaction between the LP Br→BD*N1-H, LP Br→BD*N1-C2 and LP O7→BD*C2-H. Polarizable continum model calculation revealed that aqueous phase could extremely weaken the impact of imidazolium bromide ionic liquids on the structure and property of cytosine.
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