酰胺类蚊虫驱避化合物与引诱物氨分子缔合作用的计算

›› 2015, Vol. 58 ›› Issue (6): 642-649.

酰胺类蚊虫驱避化合物与引诱物氨分子缔合作用的计算

许锡招¹, 宋杰², 王鹏¹, 范国荣¹, 陈金珠¹, 陈尚钘¹, 王宗德^1,*

（1. 江西农业大学林学院, 国家林业局/江西省樟树工程技术研究中心, 南昌 330045;  2. Department of Chemistry and Biochemistry, University of MichiganFlint, Flint 485002, USA）

出版日期:2015-06-20 发布日期:2015-06-20
作者简介:许锡招, 男, 1989年生, 江西萍乡人, 硕士研究生, 从事植物源卫生杀虫化学品的研究, E-mail: xizhaoxu@163.com

Calculation of the association between amide mosquito repellents and ammonia

XU Xi-Zhao¹, SONG Jie², WANG Peng¹, FAN Guo-Rong¹, CHEN Jin-Zhu¹, CHEN Shang-Xing¹, WANG Zong-De^1,*

(1. College of Forestry, Jiangxi Agricultural University, Camphor Tree Engineering and Technology Research Center for State Forestry Administration and Jiangxi Province, Nanchang 330045, China; 2. Department of Chemistry and Biochemistry, University of MichiganFlint, Flint 485002, USA)

Online:2015-06-20 Published:2015-06-20

摘要/Abstract

摘要： 【目的】为了探究驱避机理，此前选择萜类驱避化合物及与DEET(避蚊胺)具有类似结构的酰胺类驱避化合物，开展了驱避化合物与引诱气味组分(L-乳酸、羧酸等)缔合作用对驱避活性影响的研究。为了扩大驱避化合物的类型，本研究选择另外一组43个酰胺类驱避化合物，计算了它们与蚊虫引诱物氨之间的双分子缔合作用，以及该缔合作用对驱避活性的影响，从而为驱避机理研究提供帮助。【方法】用Gaussian 03软件优化驱避化合物单体和双分子缔合体的三维结构式；通过Ampac和Codessa软件建立结构与驱避活性之间的定量构效关系模型。【结果】驱避化合物与氨分子的缔合距离、角度和缔合能量分别是2.2~3.0 Å, 128~180°和14~25 kJ/mol；最佳四参数模型中 R²为0.8987，其中2个参数来自驱避化合物单体，分别是(1/6)X GAMMA polarizability (DIP)和ESP-minimum net atomic charge for an H atom，另外2个参数来自双分子缔合体，分别是ESP-DPSA-2 difference in CPSAs (PPSA2-PNSA2) ［Quantum-Chemical PC］和Minimum valency of a C atom。模型检验中训练集和测试集的相关系数平方的平均值分别为0.9013和0.8666。【结论】驱避化合物与氨分子之间存在弱氢键力缔合作用，驱避化合物分子的极化度及其与氨分子之间的极性相互作用、缔合体中分子间键相互作用及其电荷分布均对驱避活性产生显著影响，说明双分子缔合对驱避活性具有显著影响。模型检验表明最佳四参数模型具有良好的稳定性和预测能力。本研究可为寻找新型蚊虫驱避剂和揭示蚊虫驱避剂的作用机理提供参考。

关键词: 蚊虫驱避剂, 酰胺类驱避化合物, 引诱物；驱避活性, 氨分子, 缔合作用, 定量构效关系模型

Abstract: 【Aim】 The effect of association between mosquito repellents (terpenoids and DEET analogues) and attractants (L-lactic acid, carboxylic acids, etc.) was investigated in previous studies. In this study, a group of 43 amide repellents were chosen to further study bimolecular association between these repellents and ammonia as well as the effect of aggregate structures on repellency, so as to provide assistance for repellent mechanism research. 【Methods】 Geometry optimizations of the repellents and aggregate structures were done using Gaussian 03, and the QSAR model was established by Ampac and Codessa. 【Results】 Calculated results showed that the hydrogen bondings between amid repellents and ammonia were within the normal range of bond distances and bond angles (2.2-3.0 Å and 128-180°,respectively). The binding energies were 14-25 kJ/mol. The best four-parameter QSAR model had a R²value of 0.8987. These four statistic important parameters can be divided into two groups. The first two are related to repellents only, namely (1/6) X GAMMA polarizability (DIP) and ESP-minimum net atomic charge for an H atom. The other two are related to the repellent-ammonia aggregate, ESP-DPSA-2 difference in CPSAs (PPSA2-PNSA2) ［Quantum-Chemical PC］ and minimum valency of a C atom. The mean squared correlation coefficients of the training sets and the test sets were 0.9013 and 0.8666, respectively. 【Conclusion】 Weak hydrogen bonds are observed between repellents and ammonia. Polarizability of repellent molecules, dipole-dipole interactions between amide and ammonia, and charge distribution in aggregates are important factors influencing repellency. Model test shows that the four-parameter model has favorable stability and predictive ability. This study is helpful for seeking novel mosquito repellents and revealing the mechanism of mosquito repellents.

Key words: Mosquito repellents, amide repellents, attractants, repellent activity, ammonia, association, quantitative structure-activity relationship

许锡招, 宋杰, 王鹏, 范国荣, 陈金珠, 陈尚钘, 王宗德. 酰胺类蚊虫驱避化合物与引诱物氨分子缔合作用的计算[J]. , 2015, 58(6): 642-649.

XU Xi-Zhao, SONG Jie, WANG Peng, FAN Guo-Rong, CHEN Jin-Zhu, CHEN Shang-Xing, WANG Zong-De. Calculation of the association between amide mosquito repellents and ammonia[J]. , 2015, 58(6): 642-649.

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