植物杀虫剂苦皮藤素微乳剂的研制
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摘要
苦皮藤是我国较有开发潜力的杀虫植物之一。以苦皮藤素为活性成分的乳油已经实现了产业化，但由于乳油含有大量的二甲苯，施用后不可避免地要给环境带来潜在的危害。为此，研究将苦皮藤素乳油改进成水基制剂苦皮藤素微乳剂具有重要的意义。
以微乳剂的混合膜理论和R比理论为指导，在不添加助溶剂(或助表面活性剂)的情况下，首先确定阴离子组分DBS-Ca的高、中、低三个加入量，然后与不同的非离子型表面活性剂进行匹配试验。挑选在0～60℃的范围透明或半透明体系，对其助溶剂(或助表面活性剂)的品种和用量进行调整，最终研制成0.15％苦皮藤素微乳剂。0.15％苦皮藤素微乳剂的组成为：苦皮藤根皮提取物10％(以苦皮藤素V计为0.15％)，乳化剂2096，助溶剂25％，水45％，其中乳化剂为DBS-Ca和乳化剂A的混合物，二者的用量分别为5％和15％，助溶剂为甲醇。
建立了苦皮藤素微乳剂中活性成分苦皮藤素V的分析方法——制备薄层-液相色谱法(PTLC-HPLC)，方法的回收率98.5-100.1％，标准偏差0.0038，变异系数2.48％，符合常量分析的要求。以不同产地的苦皮藤素微乳剂为供试样品，3龄小菜蛾为试虫，用平行生测的方法对该仪器分析方法进行了验证，结果表明PTLC-HPLC法测定苦皮藤素V能够准确地反映制剂对小菜蛾的实际杀虫效果。
借鉴现行相关农药制剂的通用技术指标，结合苦皮藤素制剂的具体特点，制定了苦皮藤素微乳剂的产品质量标准。其技术指标为：苦皮藤素V含量≥0.15％(W／W)；外观为黄色透明液体；PH值范围为5～7；透明温度范围为-5～60℃；制剂能够和水以任意比例混溶，稀释液为透明均相体系，无悬浮物和沉淀物；反复冷冻后，制剂在室温下能自行恢复到正常状态：54±2℃的条件下，贮存两周，有效成分苦皮藤素V的分解率不大于8％。
田间药效试验结果表明：0.15％苦皮藤素微乳剂用于防治甘蓝地小菜蛾，稀释1000倍时防效可达80％，稀释500倍时防效可达90％以上，具有较好的推广使用价值。
作为一个具有现实商业意义的新产品，0.15％苦皮藤素微乳剂已申请国家发明专利(申请号：99109275.9)。
The Chinese bittersweet (Celasutrus angulatus Max.) is a potential insecticidal plant. The extracts of the root bark have been formulated to emulsifier concentration(EC), a formulation comprising 0.2% celangulin V(about 20% extract), 10% emulsifier and 70% dimethylbenzene. With respect to the use of organic solvents, these are generally disadvantageous from an environmental and cost viewpoint. To solve this problem, the microemulsion (ME) of celangulin, a new formulation that reduce the content of organic solvents, has been developed.
According to the theories of composite membrane and R-ratio, the defined concentrations of DBS-Ca in the system were 2%,5%, 10%, then different non-ionic surfactants were added respectively. Scanning at the temperature range of 0-60t, the eligible system should be transparent or semitransparent at certain point. After this system was adjusted by co-solvent or co-surfactant, the optimal system was selected finally.
The microemulsion of celangulin was obtained by providing an inert matrix composition comprising a defined mixture of a nonionic surfactant(DBS-Ca) and an anionic surfactant(emulsifier A), mixing with the extract to form a microemulsion concentrate, and diluting with water. Preferably, the aqueous microemulsion includes methanol herein as a co-solvent in the microemulsion system.
The quality control of botanical insecticide is a key role in the development of formulation. A PTLC-HPLC analytical method for celangulin V has been established. Compared with the results of a parallel bioassay, the content of celangulin V could represent the actual efficacy.
According to the related universal standard of pesticide, the quality indexes for 0.15% celangulin(ME) were established. It comprises appearance, content of celangulin V, PH value, cold stability, heat stability, and dilute stability and temperature range of transparence. The technic indexes of 0.15%celangulin(ME) are as follows:
(1) The composition should appear as a single phase without any
particulate or colloidal material or a second phase being present when viewed by the naked eye.
(2) The dispersion should remain clear and free of precipitation or flotage at the temperature range of-5'---600C.
(3) The freeze-thaw test indicates that the frozen formulation could recover independently at the room temperture.
(4) After heat storage at the temperature of 54 ± 2 0C, the decomposition rate of celangulin V should be lower than 8%.
The results of field trials showed that Plutella xylostella (L.) could be effectively controlled by spray a 1000 fold dilution of 0.15% celangulin.
As a competitive new product, the patent has been applied.
以微乳剂的混合膜理论和R比理论为指导，在不添加助溶剂(或助表面活性剂)的情况下，首先确定阴离子组分DBS-Ca的高、中、低三个加入量，然后与不同的非离子型表面活性剂进行匹配试验。挑选在0～60℃的范围透明或半透明体系，对其助溶剂(或助表面活性剂)的品种和用量进行调整，最终研制成0.15％苦皮藤素微乳剂。0.15％苦皮藤素微乳剂的组成为：苦皮藤根皮提取物10％(以苦皮藤素V计为0.15％)，乳化剂2096，助溶剂25％，水45％，其中乳化剂为DBS-Ca和乳化剂A的混合物，二者的用量分别为5％和15％，助溶剂为甲醇。
建立了苦皮藤素微乳剂中活性成分苦皮藤素V的分析方法——制备薄层-液相色谱法(PTLC-HPLC)，方法的回收率98.5-100.1％，标准偏差0.0038，变异系数2.48％，符合常量分析的要求。以不同产地的苦皮藤素微乳剂为供试样品，3龄小菜蛾为试虫，用平行生测的方法对该仪器分析方法进行了验证，结果表明PTLC-HPLC法测定苦皮藤素V能够准确地反映制剂对小菜蛾的实际杀虫效果。
借鉴现行相关农药制剂的通用技术指标，结合苦皮藤素制剂的具体特点，制定了苦皮藤素微乳剂的产品质量标准。其技术指标为：苦皮藤素V含量≥0.15％(W／W)；外观为黄色透明液体；PH值范围为5～7；透明温度范围为-5～60℃；制剂能够和水以任意比例混溶，稀释液为透明均相体系，无悬浮物和沉淀物；反复冷冻后，制剂在室温下能自行恢复到正常状态：54±2℃的条件下，贮存两周，有效成分苦皮藤素V的分解率不大于8％。
田间药效试验结果表明：0.15％苦皮藤素微乳剂用于防治甘蓝地小菜蛾，稀释1000倍时防效可达80％，稀释500倍时防效可达90％以上，具有较好的推广使用价值。
作为一个具有现实商业意义的新产品，0.15％苦皮藤素微乳剂已申请国家发明专利(申请号：99109275.9)。
The Chinese bittersweet (Celasutrus angulatus Max.) is a potential insecticidal plant. The extracts of the root bark have been formulated to emulsifier concentration(EC), a formulation comprising 0.2% celangulin V(about 20% extract), 10% emulsifier and 70% dimethylbenzene. With respect to the use of organic solvents, these are generally disadvantageous from an environmental and cost viewpoint. To solve this problem, the microemulsion (ME) of celangulin, a new formulation that reduce the content of organic solvents, has been developed.
According to the theories of composite membrane and R-ratio, the defined concentrations of DBS-Ca in the system were 2%,5%, 10%, then different non-ionic surfactants were added respectively. Scanning at the temperature range of 0-60t, the eligible system should be transparent or semitransparent at certain point. After this system was adjusted by co-solvent or co-surfactant, the optimal system was selected finally.
The microemulsion of celangulin was obtained by providing an inert matrix composition comprising a defined mixture of a nonionic surfactant(DBS-Ca) and an anionic surfactant(emulsifier A), mixing with the extract to form a microemulsion concentrate, and diluting with water. Preferably, the aqueous microemulsion includes methanol herein as a co-solvent in the microemulsion system.
The quality control of botanical insecticide is a key role in the development of formulation. A PTLC-HPLC analytical method for celangulin V has been established. Compared with the results of a parallel bioassay, the content of celangulin V could represent the actual efficacy.
According to the related universal standard of pesticide, the quality indexes for 0.15% celangulin(ME) were established. It comprises appearance, content of celangulin V, PH value, cold stability, heat stability, and dilute stability and temperature range of transparence. The technic indexes of 0.15%celangulin(ME) are as follows:
(1) The composition should appear as a single phase without any
particulate or colloidal material or a second phase being present when viewed by the naked eye.
(2) The dispersion should remain clear and free of precipitation or flotage at the temperature range of-5'---600C.
(3) The freeze-thaw test indicates that the frozen formulation could recover independently at the room temperture.
(4) After heat storage at the temperature of 54 ± 2 0C, the decomposition rate of celangulin V should be lower than 8%.
The results of field trials showed that Plutella xylostella (L.) could be effectively controlled by spray a 1000 fold dilution of 0.15% celangulin.
As a competitive new product, the patent has been applied.
引文
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2．陈万义，王明安．对我国植物源农药研究中几个问题的思考．第二届全国植物源农药暨第六届药剂毒理学术讨论会论文集．陕西·杨凌，2001
3．陈福良等．5％烯唑醇微乳剂的研制．农药，2001，40(3)：12～13
4．胡兆农，吴文君，姬志勤．苦皮藤杀虫生物活性的季节性和地域性变化．中国化工学会农药专业委员会第九届年会论文集．上海，1998：517～518
5．康卓．中国生物源农药产业化进展．农药，2001，40(3)：4
6．姬志勤，吴文君，胡兆农．植物杀虫剂苦皮藤有效成分苦皮藤素V的光稳定性研究．中国化工学会农药专业委员会第九届年会论文集．上海，1998
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