含取代2-苯基吡啶基团的甲氧基氨基甲酸酯类化合物的合成及杀螨活性

以取代2-溴吡啶和羟基苯硼酸为原料,经Suzuki偶联和亲核取代两步反应合成了9个未见报道的含取代2-苯基吡啶基团的甲氧基氨基甲酸酯类化合物,其结构均经红外光谱、核磁共振氢谱及质谱(ESI-MS)表征。初步生物活性测定结果表明:在500 mg/L下,部分化合物对朱砂叶螨Tetranychus cinnabarinus的致死率达100%,具有作为杀螨剂先导结构的潜力。     

Efficacy of Chinese Herbal Medicine Canine Acariasis Spirit on Demodex canis

In order to screen the Chinese herbal medicine for the treatment of Demodex canis, canine acariasis spirit was prepared by Foeniculum vulgare, Fructus cnidii and Bauhinia by water alcohol precipitation and distillation extraction methods. To observe the effect on Demodex canis, canine acariasis spirit was set to high, medium and low concentrations, the content of crude drug were 2.0, 1.0 and 0.5 g/mL, respectively. The experiment of killing Demodex canis was carried out by drop method. On this basis, 12 dogs inoculated with Demodex canis were treated. In order to verify the therapeutic effect, 45 clinically diagnosed dogs with Demodex canis were divided into three groups. The results showed that 3 doses of the traditional Chinese medicine canine acariasis spirit all had strong inhibition effect to kill mites, the high dose group could completely kill Demodex canis only 4 h after treatment, the action of 1% ivermectin control group was 8 h after treatment; 3 weeks later, a large number of new hair grew, rash and skin nodules disappeared, the skin lesion had healed in the affected area of high dose group, in 1% ivermectin treatment group, the dog skin improved, only a small amount of new hair grew, it couldn't cure standard; In the high and middle dose group, the average number of the ratio of skin scraping mites and the recurrence rate after drug withdrawal was 0 in one month later; The average number of mites proportion and recurrence rates of skin scrapings in 1% ivermectin treatment group were 10.63% and 9.17% in one month later; After 3 weeks of treatment, the total average eggs negative rate, cure rate and average cure days were 100.00%, 93.33% and 19.56 d in high dose traditional Chinese medicine canine acariasis spirit and 1% ivermectin combined treatment group, the results were better than the traditional Chinese medicine canine acariasis spirit and 1% ivermectin alone treatment group. The results showed that the effect of the high dose group self-made Chinese medicine canine acariasis spirit on killing Demodex canis in vitro, inoculation of Demodex canis and clinical therapeutic effect of natural infection cases were significantly better than 1% ivermectin control group, canine acariasis spirit as a traditional Chinese medicine preparation would have a good market development prospects.     

11种丙基酚类物质对朱砂叶螨的杀螨活性

分别采用玻片浸渍法和叶片浸渍法在室内测定了11种丙基酚类物质对朱砂叶螨的杀螨作用,结果表明,百里香酚、香芹酚、丁香酚和3-甲基-4-异丙基苯酚等4种酚类物质对朱砂叶螨具有很好的触杀作用,24 h的校正死亡率均在90以上;百里香酚对朱砂叶螨的卵孵化具有明显的影响,处理后4 d的卵孵化率仅为16.22%,显著低于对照及其它处理;产卵抑制试验显示百里香酚、香芹酚和丁香酚对朱砂叶螨具有显著的产卵抑制作用,其抑制率均在80%以上。     

5种植物提取物对朱砂叶螨的触杀活性测定

为筛选高效的植物源杀螨活性物质,采用玻片浸渍法测定了泽漆、牛至、车前草、龙葵和铁苋5种植物乙醇提取物对朱砂叶螨的触杀活性。结果表明:当提取物质量浓度为2 mg/mL时,铁苋乙醇提取物对朱砂叶螨的触杀效果在24 h和48 h均极显著于其他4种植物(P0.01),校正死亡率分别为33.63%和85.21%。根据初筛结果对铁苋进行不同极性溶剂的生物活性测定,得到氯仿提取物杀螨活性(48 h)极显著高于石油醚和乙醇提取物(P0.01),校正死亡率为90.28%。进一步采用喷雾法对铁苋氯仿提取物进行毒力测定,结果表明随着触杀时间的延长,LC50逐渐降低,在处理48 h时LC50最小,为2.81 mg/mL。由此可知:铁苋氯仿提取物有较高的杀螨活性。研究为开发高效的植物源杀螨剂提供理论依据。     

中药植物丁香杀虫杀螨活性研究

系统研究了中药植物丁香的杀虫和杀螨活性。采用正己烷、苯、乙醚、甲醇和水对丁香进行顺序提取,分别测定提取物对朱砂叶螨和玉米象等供试生物的活性,结果表明：丁香的正己烷提取物24h和72h对朱砂叶螨的致死中浓度(LC50)分别为1．5333和0．5796g／L;苯的提取物24h和72h对朱砂叶螨的致死中浓度(LC50)分别为4.4393和1．3537g／L;丁香的正己烷提取物熏蒸处理7d,对玉米象的校正死亡率达94．44％。     

8种中药提取物对朱砂叶螨触杀活性的研究

采用玻片浸渍法测定了24种植物粗提物对朱砂叶螨的杀螨活性。结果表明：当提取物质量浓度为2mg/mL时,木鳖子和石楠叶的甲醇粗提物,木鳖子、鹤虱、石楠叶和蛇莓的氯仿粗提物,急性子和木鳖子的石油醚粗提物对朱砂叶螨成虫有较好的触杀活性。其中致死率最高的为木鳖子的石油醚粗提物,致死率为77.52%;瓦松的甲醇粗提物对螨的致死率最低,为9.52%。根据初步筛选结果,选取急性子的石油醚粗提物和木鳖子的石油醚、氯仿粗提物做进一步的毒力测定,结果表明毒性最强的为木鳖子的石油醚粗提物,其LC50值为0.539 5 mg/mL。     

香豆素类化合物对朱砂叶螨的触杀活性及定量构效关系研究

香豆素类化合物是自然界广泛存在的一类具有苯并α-吡喃酮结构的天然化合物,具有抗癌、抗菌、抗炎和抗氧化等生理活性,同时也具有良好的杀虫、杀菌等农用活性。近年来研究表明,香豆素类化合物的杀螨活性更为突出,而且具有独特的作用靶标,具有开发成新型杀螨剂的潜力。本文综述了香豆素类化合物及其衍生物的杀虫、杀螨和抑菌活性,重点介绍了具有杀螨活性的香豆素类化合物的结构修饰、构效关系以及东莨菪内酯等对朱砂叶螨Tetranychus cinnabarinus的作用机制,明确其杀螨活性的主要作用靶标是新型的钙离子通道相关的G蛋白偶联神经肽受体 (TcGPCR)。这些研究进展为以香豆素类化合物为模板、以钙离子通道为靶标的新型植物性杀虫、杀螨剂的创制提供了重要基础。     

含苯乙酮结构片段的吩嗪-1-羧酸酯类衍生物的合成及生物活性

为进一步提高蛇床子素的利用价值,设计合成了26个含有1,3,4-噁二唑-2-硫基片段的新型蛇床子素类衍生物( 6a ~ 6z ),并测定了其杀虫、杀螨活性,同时通过扫描电子显微镜进一步研究了化合物 6h 对朱砂叶螨Tetranychus cinnabarinus体壁表皮角质层的影响。结果表明：化合物 6h (R=3-OCH₃Ph) 对朱砂叶螨雌成螨的杀螨活性最高,其72 h LC₅₀值为0.466 mg/mL,是蛇床子素 (LC₅₀值1.200 mg/mL) 的2.6倍;化合物 6u (R=4-CF₃Ph) 和 6v (R=3-CNPh) 对3龄小菜蛾幼虫的杀虫活性最优,48 h LC₅₀值分别为0.617和0.853 mg/mL,其中化合物 6u 的杀虫活性是蛇床子素 (LC₅₀值1.503 mg/mL) 的2.4倍。扫描电子显微镜结果显示,经化合物 6h 处理后,朱砂叶螨雌成螨体壁角质层在24 h内出现皱褶塌陷,且症状随时间推移明显加重。该研究结果可为蛇床子素类衍生物作为杀螨剂和杀虫剂的应用提供参考。     

白花丹根提取物的杀螨活性

研究了白花丹Plumbago zeylanica L. 根提取物对柑桔全爪螨的杀螨活性,发现其具有优良的杀螨、杀卵和产卵抑制活性.白花丹根先经甲醇冷浸提取,然后用石油醚萃取甲醇提取物,所得石油醚萃取物的12、24h杀螨致死中浓度(LC50)分别为2.52、2.12mg/ml, 产卵抑制中浓度(ODC50)分别为1.39、1.52mg/ml,杀卵LC50为1.04mg/ml.石油醚萃取物经硅胶柱层析后,以PE5-9馏份的活性最高,1mg/ml浓度下,杀螨率和杀卵率与白花丹素(plumbagin)标样在P=0.05水平均无显著差异.PE5-9馏份 12、24h的杀成螨LC50分别为0.71、0.67mg/ml,杀卵LC50为0.66mg/ml.不同溶剂展开系统薄层层析和GC-MS结果表明,该植物中的杀螨活性主要成分为白花丹素.