植物抗虫活性的研究在我国由来已久，且抗虫植物种类繁多，资源丰富。其中，芸香科花椒属植物在防控中药材仓储害虫中的应用历史悠久。该属植物在抗虫方面具有很大的研究和开发应用价值。 为充分开发和利用花椒属植物的药用和非药用部位，揭示该属植物代谢组分的抗虫活性，本研究以花椒属植物为研究对象，结合现代科技手段，开展了花椒属植物代谢组分防控药材仓储害虫赤拟谷盗（Tribolium castanenum）和烟草甲（Lasioderma serricorne）的研究并探讨了其构效关系。以下是本课题主要研究内容与成果： 1. 样本筛选。本研究将赤拟谷盗和烟草甲成虫作为靶标昆虫，分别对花椒属7种药用植物的挥发油部分和甲醇提取物部分进行了初步筛选。结果显示，挥发油部分和甲醇提取物部分对靶标昆虫表现出不同程度的防控作用。对于挥发油，竹叶花椒挥发油对赤拟谷盗的半数致死浓度最低，为2.06 mg/L air；刺异叶花椒挥发油对烟草甲的半数致死剂量最低，为3.40 μg/头；驱避活性中，刺异叶花椒挥发油在浓度15.73 nL/cm2，驱避4h后，对赤拟谷盗的驱避率仍然高达100%。对于甲醇提取物，2000 ppm的花椒、竹叶花椒和刺异叶花椒甲醇提取物对赤拟谷盗的拒食率均在45%以上。此外，本研究通过GC-MS分析了挥发油的化学组成成分，结合1H-NMR、HPLC指纹图谱初步判定了甲醇提取物的化学组分类型，根据活性和化学成分间的关系，进一步指导了化合物的分离。 2. 化学成分研究。基于谱效关系的样本筛选研究，本研究对优选出的花椒、竹叶花椒、刺异叶花椒挥发油和甲醇提取物进行化学分离纯化，结合理化性质和光谱方法（NMR、HR-ESI-MS）共解析出63个单体化合物，其中新化合物2个（6-(2’,3’-dihydroxy-3’-methylbutyl)-7-hydroxyl-8-(3”-methyl-2”-butenyl)-2H-1-benzopyran-2-one (17)，6-(2’-hydroxyl-3’-methyl-3’-butenyl)-7-methoxyl-8-(3”-methyl-2”-butenyl)-2H-1-benzopyran-2-one (18)），从花椒属植物中首次分离得到16个化合物（化合物2，3，7，9，10，14，15，17，18，26，28-31，47，49），除此之外，从花椒植物中首次分离4个化合物（化合物1，4-6），从竹叶花椒首次分离7个化合物（化合物12，27，33-35，38，45），从刺异叶花椒中首次分离化合物2个（化合物21，25）。其中，包括10个单萜、倍半萜类化合物（化合物1-10），19个香豆素类化合物（化合物11-29），15个木脂素类化合物（化合物30-44）。结合NMR核磁共振波谱数据，分别对香豆素和木脂素等系列化合物的谱学特征进行了分析总结，为花椒属植物提供丰富化学信息的同时，也为其抗虫活性的研究提供了物质基础。 3. 单体化合物活性研究。本研究将烟草甲、赤拟谷盗作为供试昆虫，对分离得到的单体化合物进行抗虫活性评价。结果显示，挥发油中单萜类化合物1（LC50 = 5.47 mg/L air）对赤拟谷盗的熏蒸活性最强，化合物6（LC50 = 1.21 mg/L air）对烟草甲的熏蒸活性最强，然而，各单体化合物对两种试虫的驱避活性差异很大；甲醇提取物中木脂素类化合物39（EC50 = 25.64 ppm）对赤拟谷盗的拒食活性最强。 4. 构效关系分析。香豆素类化合物的拒食活性结果显示，香豆素中环氧状结构的出现，如呋喃环等，可以增强其拒食活性；就取代基来讲，异戊烯基的出现，也可以增强香豆素类化合物对赤拟谷盗的拒食活性。从木脂素类化合物的拒食活性结果分析，亚甲二氧基作为活性取代基，在单体化合物对赤拟谷盗的拒食活性上发挥关键性作用，且该取代基的数量越多，化合物对赤拟谷盗的拒食活性越强。 本研究结果为经典传统药材养护方法“对抗同贮法”提供了理论依据，为其科学应用提供了丰富优质的植物资源，同时也为植物资源的综合开发与利用提供了新思路。

Research on plant-derived insect-resistant activity has been a hot topic in China for a long time, and plants with anti-insect activity are various and abundant. Among them, plants from Rutaceae family, Zanthoxylum genus, have a long history in the prevention and control of traditional Chinese medicine storage insects. Plants from Zanthoxylum genus have potential research value and broad prospects for the development and application in the research of insect resistance. To fully exploit and comprehensively utilize the medicinal non-medicinal parts of the plants form Zanthoxylum genus, and reveal the anti-insect activity of metabolic components, this project took some plants of Zanthoxylum genus as the research object. Combining with modern scientific and technological means, metabolic components against Tribolium castanenum and Lasioderma serricorne were found and their chemical structure-activity relationship was investigated. Here follows the main research contents and achievements: 1. Sample screening Based on the insects of T. castanenum and L. serricorne, the volatile oil fraction and methanol extract fraction of seven kinds of plants from Zanthoxylum genus were screened, respectively. The results showed that fractions form volatile oils and methanol extracts exhibited different levels of prevention and control against two target insects. Among seven volatile oils, Zanthoxylum armatum showed strong fumigant activity against T. castanenum with the lowest LC50 of 2.06 mg/L air. And, Zanthoxylum dimorphophyllum spinifolium exhibited strong contact activity against L. serricorne with the lowest LD50 of 3.40 μg/adult. On repellent activity test, Z. dimorphophyllum spinifolium showed 100% repellent rate against T. castanenum after four hours exposure at the concentration of 15.73 nL/cm2. For the methanol extracts, Z. bungeanum, Z. armatum and Z. dimorphophyllum spinifolium showed strong antifeedant activities against T. castanenum with antifeedant index above 45%. In addition, chemical constituents of volatile oils were analyzed by GC-MS and chemical composition of methanol extracts were initially analyzed by 1H-NMR and HPLC. The separation and identification of compounds were guided according to the relationship between activity and chemical composition. 2. Constituents study Based on the study of spectrum-efficiency relationship, 63 compounds were isolated, purified and finally identified from Z. bungeanum, Z. armatum and Z. dimorphophyllum spinifolium combining with physicochemical properties and spectroscopic methods (NMR, HR-ESI-MS). Among them, two were new compounds (compounds 6-(2’,3’-dihydroxy-3’-methylbutyl)-7-hydroxyl-8-(3”-methyl-2”-butenyl)-2H-1-benzopyran-2-one (17)，6-(2’-hydroxyl-3’-methyl-3’-butenyl)-7-methoxyl-8-(3”-methyl-2”-butenyl)-2H-1-benzopyran-2-one (18)). Sixteen compounds were first isolated from Zanthoxylum genus (compounds 2, 3, 7, 9, 10, 14, 15, 17, 18, 26, 28-31, 47, 49). In addition, four compounds (1, 4-6) were isolated from Z. bungeanum for the first time, seven compounds (12, 27, 33-35, 38, 45) were isolated from Z. armatum for the first time, and two compounds (21, 25) were isolated from Z. dimorphophyllum spinifolium for the first time. There were ten terpenoids (compounds 1-10), nineteen coumarins (compounds 11-29), and fifteen lignans (compounds 30-44). Comparing with NMR spectroscopy data, the nuclear magnetic resonance characteristic of coumarins and lignans were analyzed and summarized, respectively, which provided rich chemical information for Zanthoxylum genus, as well as provided material basis for anti-insect activity research. 3. Bioactivities of compounds Anti-insect activity of chemical compounds were measured. The results showed that compound 1, as monoterpenoids, showed the highest fumigant activity (LC50 = 5.47 mg/L air) against T. castanenum. And, another monoterpenoids, compound 6 showed the highest fumigant activity (LC50 = 1.21 mg/L air) against L. serricorne. While, the repellent activity of various compounds on both two insects varied greatly. On antifeedant activity test, lignan 39 showed the highest antifeedant activity (EC50 = 25.64 ppm) against T. castanenum. 4. Structure-function correlation properties Antifeedant activities of coumarins showed that the appearance of epoxy-like structures in coumarin, such as furan ring, could increase the antifeedant activity of the compounds against T. castanenum. In terms of substituents, the occurrence of isopentenyl group could enhance the antifeedant activity of coumarin against T. castanenum. According to the antifeedant activity of lignan compounds, methylenedioxy, as a reactive group, played a key role in the antifeedant activity of compounds against T. castanenum. And the more group of methylenedioxy it has, the stronger antifeedant activity it exhibits. The results of this project provided theoretical basis for the classic traditional herbal medicine conservation method of “antagonistic storage”, which provided abundant and high-quality plant resources for its scientific application, and it also provided a new idea for the comprehensive development and utilization of plant resources.