Spinosad 多杀霉素, 多杀菌素, 多杀菌

多杀霉素

多杀霉素饵剂 (猎蝇)多杀霉素又名多杀菌素(Spinosad)是在刺糖多胞菌(Saccharopolyspora spinosa)发酵液中提取的一种大环内酯类无公害高效生物杀虫剂。产生多杀菌素的亲本菌株土壤放线菌多刺糖多孢菌（Saccharopolyspora spinosa Metrz & Yao）最初分离自加勒比的一个废弃的酿酒场。美国陶氏益农公司（现为陶氏农业科学公司）的研究者发现该菌可以产生杀虫活性非常高的化合物，实用化的产品是spinosynA和spinosynB的混合物，故称其为spinosad。

多杀霉素又名多杀菌素(Spinosad)是在刺糖多胞菌(Saccharopolyspora spinosa)发酵液中提取的一种大环内酯类无公害高效生物杀虫剂。产生多杀菌素的亲本菌株土壤放线菌多刺糖多孢菌（Saccharopolyspora spinosa Metrz & Yao）最初分离自加勒比的一个废弃的酿酒场。美国陶氏益农公司（现为陶氏农业科学公司）的研究者发现该菌可以产生杀虫活性非常高的化合物，实用化的产品是spinosyn A和spinosyn D的混合物，故称其为spinosad。多杀霉素的作用方式新颖，可以持续激活靶标昆虫乙酰胆碱烟碱型受体，但是其结合位点不同于烟碱和吡虫啉。多杀霉素也可以影响GABA受体，但作用机制不清。目前还不知道是否与其他类型的杀虫剂有交叉抗性。这些化合物可以引起靶标植食性昆虫如毛虫、潜叶虫、蓟马、和食叶性甲虫迅速死亡，尽管管理部门强烈要求在抗性未出现时使用，该化合物的中度残留活性降低了抗性和群发生的可能性。当以12—150g/hm应用时，未发现有药害。
ISO通用名称：spinosad
CIPAC数字代号：636

结构式
Spinosyn A：R1=N(CH3)2，R2=H，R3=CH3
Spinosyn D：R1=N(CH3)2，R2=CH3，R3=CH3
实验式：Spinosyn A：C41H65NO10、Spinosyn D：C42H67NO10
相对分子质量（按1999年国际原子质量计）：Spinosyn A：731.98、Spinosyn D：746
生物活性：杀虫
熔点（℃）：Spinosyn A：84.0～99.5、Spinosyn D：161.5～170
蒸气压（20℃）：1.3×10－10Pa
溶解度：水235mg/L（PH=7）;能以任意比例与醇类、脂肪烃、芳香烃、卤代烃、酯类、醚类和酮类混溶
稳定性：对金属和金属离子在28d内相对稳定。在环境中通过多种途径降解，主要是光降解和微生物降解，最终变为碳、氢、氧、氮等自然成分。见光易分解，水解较快，水中半衰期为1天；在土壤中半衰期9-10天。
其它名称：菜喜，催杀

作用特点
它的作用机理被认为是烟酸乙酰胆碱受体的作用体，可以持续激活靶标昆虫乙酰胆碱烟碱型受体，但是其结合位点不同于烟碱和吡虫啉。多杀菌素也可以影响GABA受体，但作用机制不清。可使害虫迅速麻痹、瘫痪，最后导致死亡。其杀虫速度可与化学农药相媲美。安全性高，且与目前常用杀虫剂无交互抗性为低毒、高效、低残留的生物杀虫剂，既有高效的杀虫性能，又有对有益虫和哺乳动物安全的特性， 最适合无公害蔬菜、水果生产应用。是一种低毒、高效、广谱的杀虫剂。
毒性：
原药对雌性大鼠急性口服LD50>5000毫克/千克，雄性为3738毫克/千克，小鼠>5000毫克/千克，兔急性经皮LD50>5000毫克/千克。对皮肤无刺激，对眼睛有轻微刺激，2天内可消失。多杀菌素在环境中可降解，无富集作用，不污染环境。

作用机理
对害虫具有快速的触杀和胃毒作用，对叶片有较强的渗透作用，可杀死表皮下的害虫，残效期较长，对一些害虫具有一定的杀卵作用。无内吸作用。能有效的防治鳞翅目、双翅目和缨翅目害虫，也能很好的防治鞘翅目和直翅目中某些大量取食叶片的害虫种类，对刺吸式害虫和螨类的防治效果较差。对捕食性天敌昆虫比较安全，因杀虫作用机制独特，目前尚未发现与其他杀虫剂存在交互抗药性的报道。对植物安全无药害。适合于蔬菜、果树、园艺、农作物上使用。杀虫效果受下雨影响较小。

分析方法
高效液相色谱定量分析方法.以甲醇+乙腈+水为流动相,C18和紫外检测器进行测定。
制剂：2.5%、48%悬浮剂，并有BT及部分化学农药与之复配的产品。
使用方法：
1. 蔬菜害虫防治小菜蛾，在低龄幼虫盛发期用2.5%悬浮剂1000-1500倍液均匀喷雾，或每667平方米用2.5%悬浮剂33-50毫升对水20-50千克喷雾。
2. 防治甜菜夜蛾，于低龄幼虫期，每667平方米用2.5%悬浮剂50-100毫升对水喷雾，傍晚施药效果最好。
3. 防治蓟马，于发生期，每667平方米用2.5%悬浮剂33-50毫升对水喷雾，或用2.5%悬浮剂1000-1500倍液均匀喷雾，重点在幼嫩组织如花、幼果、顶尖及嫩梢等部位。

注意事项
1.可能对鱼或其他水生生物有毒，应避免污染水源和池塘等。
2.药剂贮存在阴凉干燥处。
3.最后一次施药离收获的时间为7天。避免喷药后24小时内遇降雨。
4. 应注意个人的安全肪护，如溅入眼睛，立即用大量清水冲洗。如接触皮肤或衣物,用大量清水或肥皂水清洗。如误服不要自行引吐，切勿给不清醒或发生痉挛患者灌喂任何东西或催吐，应立即将患者送医院治疗。

spinosad
See also The BioPesticide Manual, 2nd Ed., entry 2:144
Insecticide
IRAC 5; spinosyn

NOMENCLATURE
Common name spinosad (BSI, pa ISO, ANSI)
IUPAC name A mixture of (2R,3aR,5aR,5bS,9S,13S,14R,16aS,16bR)-2-(6-deoxy-2,3,4-tri-O-methyl-a-L-mannopyranosyloxy)-13-(4-dimethylamino-2,3,4,6-tetradeoxy-b-D-erythopyranosyloxy)-9-ethyl-2,3,3a,5a,5b,6,7,9,10,11,12,13,14,15,16a,16b-hexadecahydro-14-methyl-1H-8-oxacyclododeca[b]as-indacene-7,15-dione and (2R,3aS,5aR,5bS,9S,13S,14R,16aS,16bR)-2-(6-deoxy-2,3,4-tri-O-methyl-a-L-mannopyranosyloxy)-13-(4-dimethylamino-2,3,4,6-tetradeoxy-b-D-erythopyranosyloxy)-9-ethyl-2,3,3a,5a,5b,6,7,9,10,11,12,13,14,15,16a,16b-hexadecahydro-4,14-dimethyl-1H-8-oxacyclododeca[b]as-indacene-7,15-dione in the proportion 50-95% to 50-5%
Chemical Abstracts name 2-[(6-deoxy-2,3,4-tri-O-methyl-a-L-mannopyranosyl)oxy]-13-[[5-(dimethylamino)tetrahydro-6-methyl-2H-pyran-2-yl]oxy]-9-ethyl-2,3,3a,5a,5b,6,9,10,11,12,13,14,16a,16b-tetradecahydro-14-methyl-1H-as-indaceno(3,2-d)oxacyclododecin-7,15-dione (spinosyn A), mixture with 2-[(6-deoxy-2,3,4-tri-O-methyl-a-L-mannopyranosyl)oxy]-13-[[5-(dimethylamino)tetrahydro-6-methyl-2H-pyran-2-yl]oxy]-9-ethyl-2,3,3a,5a,5b,6,9,10,11,12,13,14,16a,16b-tetradecahydro-4,14-dimethyl-1H-as-indaceno(3,2-d)oxacyclododecin-7,15-dione (spinosyn D)
CAS RN [168316-95-8]; [131929-60-7] spinosyn A; [131929-63-0] spinosyn D Development codes XDE-105; DE-105 (both Dow)

PHYSICAL CHEMISTRY
Composition Tech. is >90%, composed of 50-95% spinosyn A and 50-5% spinosyn D. Mol. wt. 732.0 (spinosyn A); 746.0 (spinosyn D) M.f. C41H65NO10 (spinosyn A); C42H67NO10 (spinosyn D) Form Light grey to white crystals (tech.). M.p. 84-99.5 °C (spinosyn A); 161.5-170 °C (spinosyn D) V.p. 3.0 ´ 10-5 mPa (25 °C) (spinosyn A); 2.0 ´ 10-5 mPa (25 °C) (spinosyn D) KOW logP = 2.8 (pH 5), 4.0 (pH 7), 5.2 (pH 9) (spinosyn A); logP = 3.2 (pH 5), 4.5 (pH 7), 5.2 (pH 9) (spinosyn D) S.g./density 0.512 (bulk, 20 °C) Solubility Spinosyn A: In water 89 ppm (distilled water), 235 ppm (pH 7) (both 20 °C). In acetone 16.8, acetonitrile 13.4, dichloromethane 52.5, hexane 0.448, methanol 19.0, n-octanol 0.926, toluene 45.7 (all in g/l, 20 °C). Spinosyn D: In water 0.5 ppm (distilled water), 0.33 ppm (pH 7) (both 20 °C). In acetone 1.01, acetonitrile 0.255, dichloromethane 44.8, hexane 0.743, methanol 0.252, n-octanol 0.127, toluene 15.2 (all in g/l, 20 °C). Stability Stable to hydrolysis at pH 5 and 7; DT50 (pH 9) 200 d (spinosyn A), 259 d (spinosyn D). Aquatic photodegradation DT50 (pH 7) 0.93 d (spinosyn A), 0.82 d (spinosyn D). pKa 8.1 (spinosyn A); 7.87 (spinosyn D)

COMMERCIALISATION
Production Derived from the actinomycete Saccharopolyspora spinosa. Following fermentation, spinosad is obtained from a whole broth extraction. History The spinosyns first identified, in a soil sample, by Eli Lilly & Co. (agrochemical interests now Dow AgroSciences) in 1982. Commercially introduced during 1997. Patents US 5202242; EP 375316 Manufacturers Dow AgroSciences

APPLICATIONS
Biochemistry Activation of the nicotinic acetylcholine receptor, but at a different site from nicotine or imidacloprid. Mode of action Active by contact and ingestion; causes paralysis. Uses For control of pest Lepidoptera (e.g. Ostrinia nubilalis, Helicoverpa zea, Trichoplusia ni, Plutella xylostella, Spodoptera spp., Heliothis spp., Pieris rapae, Keiferia lycopersicella, Lobesia botrana), thrips (e.g. Frankliniella occidentalis, Thrips palmi), flies (e.g. Liriomyza spp., Ceratitis capitata), beetles (e.g. Leptinotarsa decemlineata) and grasshoppers in cotton, row crops, vegetables, and fruits, at 4.8-36 g/hl. Also used for urban pest control (e.g. Agrotis ipsilon, Spodoptera spp., Parapediasia teterella) in turf and ornamentals, for structural control of drywood termites (e.g. Cryptotermes brevis, Incisitermes snyderi), and for fire ant (Solenopsis spp.) control. Effective as a bait for fruit flies (Ceratitis spp., Bactrocera spp., etc) and some ants (Solenopsis spp.).Under development for use on livestock animals for control of chewing and sucking lice (e.g. Linognathus vituli, Bovicola ovis, Solenopotes capillatus) and flies (e.g. Haematobia irritans, Lucilia cuprina), and in livestock premises for control of nuisance flies (e.g. Stomoxys calcitrans, Musca domestica, H. irritans). Formulation types SC; WG. Selected products: 'Conserve' (Dow AgroSciences); 'SpinTor' (Dow AgroSciences); 'Success' (Dow AgroSciences); 'Tracer' (Dow AgroSciences)

OTHER PRODUCTS
'Entrust' (Dow AgroSciences); 'Extinosad' (veterinary use) (Elanco); 'GF-120' (Dow AgroSciences); 'Justice' (Dow AgroSciences); 'Laser' (Dow AgroSciences); 'Naturalyte' (Dow AgroSciences); 'Spinoace' (Dow AgroSciences) Discontinued products: 'Spintech' * (Dow AgroSciences)

ANALYSIS
Residues by hplc or immunoassay. Details available from Dow AgroSciences.

MAMMALIAN TOXICOLOGY
Reviews FAO/WHO 92, 94 (see part 2 of the Bibliography). Oral Acute oral LD50 for male rats 3783, female rats >5000 mg/kg. Skin and eye Acute percutaneous LD50 for rabbits >2000 mg/kg. Non-irritating to skin; slight irritation to eyes (rabbits). Not a skin sensitiser (guinea pigs). Inhalation LC50 (4 h) for rats >5.18 mg/l. NOEL (13 w) for dogs 5, mice 6-8, rats 9-10 mg/kg b.w. daily. ADI (JMPR) 0.02 mg/kg b.w. [2001]; (US) 0.027 mg/kg b.w.; (Japan, Australia) 0.024 mg/kg b.w. Other Non-neurotoxic, non-mutagenic; no reproductive effects. Toxicity class WHO (a.i.) U; EPA (formulation) IV (tech.), IV ('Tracer')

ECOTOXICOLOGY
Birds Acute oral LD50 for bobwhite quail and mallard ducks >2000 mg/kg. Acute dietary LC50 for bobwhite quail and mallard ducks >5156 ppm. Fish LC50 (96 h) for rainbow trout 30, bluegill sunfish 5.9, common carp 5, Japanese carp 3.5, sheepshead minnow 7.9 mg/l. Daphnia EC50 (48 h) 14 ppm. Algae EC50 for Selenastrum capricornutum >105.5, Skeletonema costatum 0.2, Navicula pelliculosa 0.09, Anabaena flos-aquae 8.9 ppm. Other aquatic spp. EC50 (96 h) for Eastern oyster 0.3, grass shrimp >9.76 ppm. EC50 for Lemna gibba 10.6 ppm. Bees Highly toxic to honeybees when sprayed directly; topical LD50 (48 h) 0.0029 mg/bee; residues have little effect once dry. Worms LC50 (14 d) for Eisenia foetida >1000 mg/kg soil. Other beneficial spp. Non-toxic to sucking insects, predacious insects (e.g. ladybirds), lacewings, big-eyed bugs or minute pirate bugs. See also M. Miles & R. Dutton Proc. Br. Crop Prot. Conf. - Pests Dis., 2000, 1, 339.

ENVIRONMENTAL FATE
Animals Spinosad is rapidly absorbed, extensively metabolised, and eliminated mainly via urine and faeces. Metabolites include glutathione conjugates and N- and O- demethylated macrolides. No residues of spinosad were found in meat, milk or eggs. Plants On plant surfaces, DT50 1.6-16 d; degradation is mainly by photolysis. No residues of spinosad or metabolites were found in cotton seed. Soil/Environment Rapidly degraded by u.v. light and soil microbes to naturally-occurring substances. Soil DT50 for aerobic metabolism 9.4-17.3 d (spinosyn A), 14.5 d (spinosyn D); the major metabolite from spinosyn A is spinosyn B (N-demethylation product); spinosyn D is metabolised similarly. DT50 for photodegradation on soil 8.7 d (spinosyn A), 9.4 d (spinosyn D). DT50 for anaerobic aquatic metabolism 161 d (spinosyn A), 250 d (spinosyn D). Adsorption Freundlich K for spinosyn A 5.4-323; not determined for spinosyn D (expected to be less mobile); for A metabolite (spinosyn B) 4.3-179. DT50 for field dissipation is £0.5 d, with no detectable radiolabel below 24 inches.