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| 异辛基乙二胺-酰基丙氨酸型质子化离子液体的分子间氢键相互作用 | |
| 引用本文： | 刘佳鑫,徐宇,花儿. 异辛基乙二胺-酰基丙氨酸型质子化离子液体的分子间氢键相互作用[J]. 化工学报, 2020, 71(z1): 15-22. DOI: 10.11949/0438-1157.20191380 |
| 作者姓名： | 刘佳鑫 徐宇 花儿 |
| 作者单位： | 1.北方民族大学化学与化学工程学院，宁夏 银川 750021;2.北方民族大学国家民委化工技术基础重点实验室，宁夏 银川 750021;3.北方民族大学宁夏太阳能化学转化技术重点实验室，宁夏 银川 750021 |
| 基金项目： | 北方民族大学科技创新类重点科研项目 |
| 摘 要： | 利用密度泛函理论M06-2X/6-311G(d,p)方法及基组条件下，对异辛基乙二胺-酰基丙氨酸型质子化离子液体[HEtHex]+[Acylala]-(Acyl =butanoyl, hexanoyl)的几何构型进行了优化，分别得到了5种较稳定构型S1~S5。结果显示，[HEtHex][Butlala]及[HEtHex][Hexlala]的基组重叠误差校正后的分子间相互作用能(ΔE0BSSE)均在-136.14~-117.26 kcal·mol-1（1 kcal·mol-1=4.182 kJ·mol-1）范围内，其中伯胺质子化构型(S1~S3)的相互作用能(-136.14~-127.01 kcal·mol-1)大于仲胺质子化构型(S4~S5)(-119.03~-117.26 kcal·mol-1)。由于[HEtHex][Acylala]阴阳离子间发生了质子转移而形成了较强的O—H…N型氢键，引起[HEtHex]+中N—H振动频率消失，并在2400~2815 cm-1处出现了较强的O—H的伸缩振动，即以分子与分子间的作用力键合。自然键轨道及分子中原子理论计算结果显示，[HEtHex][Acylala]间所形成氢键的稳定化能主要来源于[EtHex]分子中胺基N原子的孤对电子lp(N)与[Acylala]分子中羧基的反键轨道σ*(O—H)间的相互作用。并且分子间氢键能及二阶微扰能分别在18.69 ~ 24.19 kcal·mol-1及43.58 ~57.58 kcal?mol-1范围内，属于较强类型氢键作用。 |
| 关 键 词： | 酰基氨基酸离子液体 密度泛函理论 质子转移 分子间氢键作用 |
| 收稿时间： | 2019-11-13 |
| 修稿时间： | 2019-12-19 |
Structure and hydrogen bonding study on acylamino acid protic ionic liquids composed of 2-N-ethylhexylethylenediaminim cation with acylalanineate anions |
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| LIU Jiaxin,XU Yu,HUA Er. Structure and hydrogen bonding study on acylamino acid protic ionic liquids composed of 2-N-ethylhexylethylenediaminim cation with acylalanineate anions[J]. Journal of Chemical Industry and Engineering(China), 2020, 71(z1): 15-22. DOI: 10.11949/0438-1157.20191380 | |
| Authors: | LIU Jiaxin XU Yu HUA Er |
| Affiliation: | 1.College of Chemistry and Chemical Engineering, North Minzu University, Yinchuan 750021, Ningxia, China;2.Key Laboratory of Chemical Engineering and Technology, State Ethnic Affairs Commission, North Minzu University, Yinchuan 750021, Ningxia, China;3.Ningxia Key Laboratory of Solar Chemical Conversion Technology, North Minzu University, Yinchuan 750021, Ningxia, China |
| Abstract: | The possible molecular structures S1—S5 of acylamino acid protic ionic liquids (AA-PILs) composed of 2-N-ethylhexylethylenediaminium cation coupled with acylalanineate anions forming [HEtHex][Acylala] were studied by the density functional theory at M06-2X/6-311G (d,p) level. The obtained BSSE-corrected interaction energies (ΔE0BSSE) for all the structures are in the region of -136.14~-117.26 kcal?mol-1. For each PIL, the values of ΔE0BSSE in the [HEtHex]1+[Acylala]- (S1—S3, protonated at the primary amine, -136.14—-127.01 kcal·mol-1) are larger than in the [HEtHex]2+[Acylala]- structures (S4 and S5, protonated at the secondary amine, -119.03—-117.26 kcal·mol-1). The IR results show that N—H vibration spectra is disappeared. In the meantime, the stronger O—H vibration spectra appeared in the region of 2400—2815 cm-1 since stronger O—H…N hydrogen bond was formed between [HEtHex] molecule and [Acylala] molecule. The results of natural bond orbital the stabilization energy mainly caused by the interaction between the lone pair electron lp(N) in the [EtHex] and the anti-bonding orbital σ*(O—H) in the [Acylala]: lp(N)→σ*(O—H). The hydrogen bonding energy and the second-order interaction energies are in the range of 18.69—24.19 kcal·mol-1 and 43.58—57.58 kcal?mol-1, respectively. H-bonding between [HEtHex] and [Acylala] is classified as the strong hydrogen bond. |
| Keywords: | acylamino acid protic ionic liquids density functional theory proton transfer inter molecular hydrogen bonding |
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