尼古丁-扁桃酸盐晶的制备及晶体结构分析
Preparation and Crystal Structure Analysis of Nicotine Mandelate Crystals
作者：杨 继(四川大学 化学工程学院)；缪明明(云南中烟工业有限责任公司技术中心)；吴 俊(云南中烟工业有限责任公司技术中心)；陈永宽(云南中烟工业有限责任公司技术中心)；刘志华(云南中烟工业有限责任公司技术中心)；汤建国(云南中烟工业有限责任公司技术中心)；侯 权(四川大学 化学工程学院)；索自立(四川大学 化学工程学院)；李 晖(四川大学 化学工程学院)
Author：YANG Ji(College of Chemical Engineering,Sichuan Univ)；MIAO Mingming(Research and Development Center,China Tobacco Yunnan Industry Co LTD)；WU Jun(Research and Development Center,China Tobacco Yunnan Industry Co LTD)；CHEN Yongkuan(Research and Development Center,China Tobacco Yunnan Industry Co LTD)；LIU Zhihua(Research and Development Center,China Tobacco Yunnan Industry Co LTD)；TANG Jianguo(Research and Development Center,China Tobacco Yunnan Industry Co LTD)；HOU Quan(College of Chemical Engineering,Sichuan Univ)；SUO Zili(College of Chemical Engineering,Sichuan Univ)；LI Hui(College of Chemical Engineering,Sichuan Univ)
收稿日期：2019-05-11 年卷（期）页码：2020,52(5):-
期刊名称：工程科学与技术
Journal Name：Advanced Engineering Sciences
关键字：尼古丁；扁桃酸；晶体结构；“赫希菲尔德”表面；分子间相互作用能
Key words：Nicotine; Mandelic acid; Crystal structure; Hirshfeld surface; Intermolecular interaction energy;
基金项目：中国烟草总公司科技重大专项项目“胶基型无烟气烟草制品质量稳定性关键技术研究”110201601005(2016xx-05)；云南中烟工业公司科技开发计划项目 “以舒适感和口腔健康为导向的口含烟关键技术研究”(2018CP07)
中文摘要
以制备尼古丁有机酸盐复合物并提供一种无烟气烟草制品中尼古丁新的添加形式为主要目的,利用超声加热搅拌方法合成了尼古丁-扁桃酸复合物,并在溶剂挥发条件下获得了尼古丁-扁桃酸盐晶单晶体。X-射线单晶衍射结果显示：尼古丁-扁桃酸盐晶体为正交晶系,P212121空间群,晶胞参数a = 9.5074(5),b = 12.7246(9),c = 20.4101(12),α =90,β =90,γ =90,Z =4。应用CrystalExplorer软件进一步解析其晶体结构,晶体中分子堆积方式表明,尼古丁离子与扁桃酸根离子两两紧密结合且整体形成菱形网格状结构,每个菱形格中都插入一个中性扁桃酸分子。“赫希菲尔德”表面分析显示,尼古丁-扁桃酸盐晶体中形成N2?H2...O5,O6?H6A...O5,O8?H8...N1三种氢键使得分子在该处电子密度更加密集,在基于标准距离函数的“赫希菲尔德”表面上表现为红色圆点。2-D指纹图谱说明,H原子在尼古丁-扁桃酸晶体中的分子间相互作用中起着至关重要的作用。相互作用能分析结果是：尼古丁-扁桃酸盐晶体结构中存在21种不同类型的分子间相互作用能。由于N2?H2...O5,O6?H6A...O5,O8?H8...N1氢键的存在,尼古丁离子与邻近扁桃酸离子和扁桃酸分子间的相互作用能数值最大。采用能量框架模型实现了晶体结构中相互作用能的可视化,加深了对尼古丁-扁桃酸晶体结构中分子间相互作用能的深刻理解。本研究,对其探究尼古丁化学结合形态以及在无烟气烟草制品配方设计中具有一定的理论指导和应用价值。
英文摘要
The main purpose of this study is to prepare nicotine organic salt complex and provide a new nicotine addition form in smokeless tobacco products. Nicotine-mandelic acid complexes were synthesized by ultrasonic heating and stirring, and nicotine-mandelic acid crystals were obtained. nicotine-mandelic acid crystal structure solved by SXRD belongs to orthonormal crystal system with space group P212121, the cell parameters are a = 9.5074(5), b = 12.7246(9), c = 20.4101(12), α =90, β =90, γ =90, Z =4.In the crystal structure of nicotine-mandelic acid, nicotine ion and mandelic acid ion bind tightly and form a diamond grid structure, a neutral mandelic acid molecule is inserted into each diamond lattice. According to Hirshfeld surface analysis, the H bonds of N2?H2...O5, O6?H6A...O5, O8?H8...N1 make the electron density of molecules at that point is more intensive, which leads bright red areas on Hirshfeld surfaces mapped with dnorm. 2-D fingerprints show that H plays an important role in the intermolecular interaction of nicotine-mandelic acid crystals. The result of interaction energy analysis is that 21 kinds of intermolecular interaction energies exist in nicotine-mandelic acid crystal structure. Because of the existence of N2?H2...O5, O6?H6A...O5, O8?H8...N1hydrogen bonds, the interaction between nicotine ions and neighbouringmandelic acid ions ormandelic acid molecules can be significantly greater than others.We also use the energyframe model to visualize the interaction energy in the nicotine-mandelic acid crystal structure which make us understand the interaction energy more conveniently and clearly. The results of this study have important theoretical guidance and application value for further exploring the chemical binding form of nicotine and formulation design of smokeless tobacco products.
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