›› 2014, Vol. 57 ›› Issue (9): 1025-1031.

• 研究论文 • 上一篇    下一篇

萜类驱避化合物与引诱物三分子缔合的计算研究

许锡招1, 廖圣良1, 宋杰2, 王鹏1, 范国荣1, 姜志宽3, 王宗德1,*
  

  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; 3. 南京军区疾病预防控制中心, 南京 210042)
  • 出版日期:2014-09-20 发布日期:2014-09-20
  • 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 trimolecular association between terpenoid repellents and attractants

XU Xi-Zhao1, LIAO Sheng-Liang1, SONG Jie2, WANG Peng1, FAN Guo-Rong1, JIANG Zhi-Kuan3, WANG Zong-De 1,*   

  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; 3. Center for Disease Control and Prevention of Nanjing Command, Nanjing 210042, China)
  • Online:2014-09-20 Published:2014-09-20

摘要: 【目的】目前驱避剂的作用机理研究还不理想,本研究从单个萜类驱避化合物分子与不同种类引诱气味分子同时相互缔合的角度入手,通过理论计算探究该缔合与蚊虫驱避作用的关系,从而为驱避作用机理研究提供新认识。【方法】利用Gaussian View 4.1和Gaussian 03W软件构建和优化萜类驱避化合物单体、单体与引诱物L-乳酸及氨分子同时缔合后三分子缔合体的结构,获得其最低能量结构和缔合能;通过程序Ampac 8.16将前述结构导入到程序Codessa 2.7.10,计算各类结构描述符;再利用Codessa 2.7.10的启发式方法得到一系列缔合体结构描述符与驱避活性之间的定量关系模型,并通过转折点确定、模型验证后确定最佳定量关系计算模型。【结果】三分子缔合的缔合能基本上在20~50 kJ/mol的范围,所得最佳三参数定量计算模型的R2值为0.9098,包含的3个结构描述符分别是三分子缔合体的maximum nucleophilic reactivity index for a C atom,topographic electronic index (all bonds) [Zefirov’s PC]和exchange energy + e-e repulsion for a H-O bond。【结论】萜类驱避化合物分子可同时与2个不同种类的引诱物分子发生缔合作用,该缔合作用符合氢键的能量基本特征;缔合体的碳原子最大原子核反应指数、所有键的拓扑电子指数、氢氧键电子间交换互斥能对驱避活性影响显著。这些结果初步说明萜类驱避化合物与引诱物三分子缔合作用确实存在,且该缔合作用对驱避活性具有显著影响,这为驱避机理的研究提供了新的理论依据。

关键词: 萜类驱避剂, 引诱物, 三分子缔合, 缔合能, 定量构效关系, 结构描述符

Abstract: 【Aim】 The research of repellent mechanism is still unsatisfactory. This study intends to investigate the trimolecular association between single terpenoid repellent and two different attractants, and the relationship between the trimolecular association and mosquito repellency through the theoretical calculation. The goal is to develop a new direction for the repellent mechanism research.【Methods】 Gaussian View 4.1 and Gaussian 03W softwares were used to build and optimize the structure of terpenoid repellent monomers and trimolecular complexes which comprise L-lactic acid, ammonia and repellents. The optimized structure and association energy were obtained after optimization. Ampac 8.16 was applied to import all the above structures into the Codessa 2.7.10 software. Various kinds of structural descriptors were calculated, and a series of quantitative models which imply the relationship between structural descriptor of the association and repellent activity were generated by the heuristic method encoded in Codessa 2.7.10. The best quantitative model was picked out through breaking point rule and model validation. 【Results】 The energy of trimolecular association is basically in the range of 20 to 50 kJ/mol, and the R2 of the best threeparameter quantitative model is 0.9098. Three structural descriptors contained in the model were the maximum nucleophilic reactivity index for a C atom, topographic electronic index (all bonds) [Zefirov’s PC] and exchange energy + e-e repulsion for a H-O bond.【Conclusion】 A terpenoid repellent molecule can associate with two different attractant molecules at the same time, and this trimolecular association matches the basic characteristics of hydrogen bonds. The maximum nucleophilic reactivity index for a C atom, topographic electronic index (all bonds) [Zefirov’s PC] and exchange energy + e-e repulsion for a H-O bond, which are three descriptors generated from trimolecular complexes, tightly correlate to the repellency. This research preliminarily illustrates the existence of trimolecular association between terpenoid repellents and attractants, and its influence on the repellency. The result provides a new theoretical basis for the future repellent mechanism research.

Key words: Terpenoid repellent, attractant, trimolecular association, association energy, quantitative structureactivity relationship (QSAR), structural descriptor