定量计算萜类蚊虫驱避化合物与羧酸缔合作用对其驱避活性的影响

›› 2014, Vol. 57 ›› Issue (5): 547-556.

定量计算萜类蚊虫驱避化合物与羧酸缔合作用对其驱避活性的影响

廖圣良^{1, 2}，宋杰³，范国荣¹，王鹏¹，王宗德^1,*，陈尚钘¹，姜志宽⁴，陈金珠¹

（1. 江西农业大学林学院，南昌 330045； 2. 中国林业科学研究院林产化学工业研究所，南京 210042； 3. Department of
Chemistry and Biochemistry, University of MichiganFlint, Flint 485002, USA； 4. 南京军区疾病预防控制中心，南京 210042）

出版日期:2014-05-20 发布日期:2014-05-20

Quantitative calculation of the influence of molecular association between terpenoid mosquito repellents and carboxylic acids on their repellency

LIAO Sheng-Liang^{1, 2}, SONG Jie³, FAN Guo-Rong¹, WANG Peng¹, WANG Zong-De^1,*, CHEN Shang-Xing¹, JIANG Zhi-Kuan⁴, CHEN Jin-Zhu¹

(1. College of Forestry, Jiangxi Agricultural University, Nanchang 330045, China; 2. Institute of Chemical Industry of Forestry Products, China Academy of Forestry, Nanjing 210042, China; 3. Department of Chemistry and Biochemistry, University of MichiganFlint, Flint 485002, USA; 4. Center for Disease Control and Prevention of Nanjing Command, Nanjing 210042, China)

Online:2014-05-20 Published:2014-05-20

摘要/Abstract

摘要： 【目的】驱避剂是防止蚊虫叮咬的良好个人防护用品，但其作用机理一直未被解释清楚。本研究利用化学计算手段对4种重要的人体引诱物（乙酸、丙酸、丁酸和戊酸）与22个萜类驱避化合物的缔合作用以及该作用对驱避活性的影响进行了研究，以期为蚊虫驱避机理研究提供新思路。【方法】利用GAUSS View软件构建引诱化合物分子、驱避化合物分子以及二者可能形成的缔合体结构，再利用GAUSSIAN软件优化所有结构，并计算它们的能量和各类参数；借助AMPAC和CODESSA软件计算出所有结构的描述符；以萜类驱避化合物对白纹伊蚊Aedes albopictus校正驱避率的对数值（logCRR）为活性数据，利用CODESSA软件建立描述符与驱避活性的定量构效关系模型。【结果】4种羧酸与萜类驱避化合物相互缔合的缔合能量大多在18~20 kJ/mol之间，缔合距离和角度分别在2.0~2.5 Å 和110°~180°内波动，符合氢键相互作用的特征。4个最优定量构效关系模型的R²值均大于0.9，模型中的参数都包含缔合体的描述符，表明引诱物驱避物缔合作用与校正驱避率的对数值显著相关。【结论】4种羧酸与萜类驱避化合物之间存在中等强度的氢键缔合作用，该缔合作用对驱避活性具有重要影响。研究初步揭示了引诱物驱避物缔合作用的存在，也为从新的角度研究蚊虫驱避机理提供了前期研究基础。

关键词: 萜类；蚊虫驱避剂, 羧酸, 分子缔合, 驱避活性, 定量构效关系

Abstract: 【Aim】 Mosquito repellents are a group of compounds which can protect human from mosquito biting. However, the repelling mechanisms are still unclear. In this study, theoretical calculations were applied to investigate the molecular association between four important human-derived attractants (acetic acid, propionic acid, butyric acid and pentanoic acid) and twenty-two terpenoid repellents, to find out the relationship between this kind of interaction and repellency, and so to clarify the repelling mechanisms from a new perspective.【Methods】 Structures of attractants, repellents and attractant-repellent complexes were built and optimized by GAUSS View and GAUSSIAN, and association energy and geometrical parameters were obtained. Descriptors for model building were calculated by AMPAC and CODESSA. The quantitative structure-activity relationship (QSAR) models were built to analyze the relationship between the structural descriptors and the logarithm value of the corrected repelling time (logCRR) against Aedes albopictus. 【Results】 The association energy between four carboxylic acids and twenty-two terpenoid repellents is between 18 and 20 kJ/mol, and the association distance and angle are fluctuating from 2.0 to 2.5 Å and from 110° to 180°, respectively, which exactly fit the characteristics of hydrogen bonding interaction. Four obtained QSAR models were statistically satisfying, and the R² values of any one of these four parametric models were above 0.9. Every model contained the descriptors generated from attractant-repellent complex, showing a significant correlation between attractant-repellent association and the logCRR. 【Conclusion】 Hydrogen bonding associations with moderate strength exist between four carboxylic acids and terpenoid repellents, and such kinds of associations deeply affect the repellency. This study provides a preliminary support to the existence of attractant-repellent association and sets up a foundation for the research of repelling mechanism from a new perspective.

Key words: Terpenoid, mosquito repellent, carboxylic acid, molecular association, repellency, quantitative structure-activity relationship (QSAR)

廖圣良，宋杰，范国荣，王鹏，王宗德，陈尚钘，姜志宽，陈金珠. 定量计算萜类蚊虫驱避化合物与羧酸缔合作用对其驱避活性的影响[J]. , 2014, 57(5): 547-556.

LIAO Sheng-Liang, SONG Jie, FAN Guo-Rong, WANG Peng, WANG Zong-De, CHEN Shang-Xing, JIANG Zhi-Kuan, CHEN Jin-Zhu. Quantitative calculation of the influence of molecular association between terpenoid mosquito repellents and carboxylic acids on their repellency[J]. , 2014, 57(5): 547-556.

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