松油烯-4-醇对淡色库蚊的熏蒸毒力及对其Na+ ,K+ -ATP酶的抑制作用

为进一步探讨杀虫植物砂地柏Sabina vulgaris Ant.精油中主要杀虫活性成分—松油烯-4-醇(terpinen-4-ol)对卫生害虫的生物活性,测定了该物质对淡色库蚊Culex pipiens Pallens及其Na+,K+-ATP酶活性的影响。结果表明:松油烯-4-醇对淡色库蚊具有较强的熏蒸作用,其LC50值为6.79 mg/L, 在LC80剂量下其击倒中时(KT50)为6.92 min;淡色库蚊Na+,K+-ATP酶活性测定的最佳反应条件为pH值7.42、温度35.5℃、底物浓度0.7 mmol/L;离体和活体情况下,松油烯-4-醇均可显著抑制淡色库蚊Na+,K+-ATP酶的活性,其I50值为32.02 μg/mL。Na+,K+-ATP酶可能是松油烯-4-醇对淡色库蚊的杀虫作用靶标。     

松油烯-4-醇对家蝇体内几种酶系的影响

测定了松油烯-4-醇对家蝇成虫的毒杀活性及其体内几种酶系活性的影响.结果表明:松油烯-4-醇对家蝇具有较强的触杀作用,24h的LD50为23.91μg/虫;对家蝇的致毒症状可明显地分为兴奋、痉挛、麻痹、死亡或复苏等几个阶段;对Na ,K -ATPase具有较强的抑制作用,在兴奋期、痉挛期、麻痹期和复苏期,酶抑制率分别为23.2l%、20.27%、61.84%和58.35%;离体条件下,对Na ,K -ATPase的I50为0.8379×103μg·mL-1;对AChE有一定的抑制作用;可激活酯酶,在复苏期,酶比活力为对照的1.42倍.     

4-甲基-1,2,3-噻二唑-5-甲酸芳酯的合成及生物活性

为了寻找高效广谱的植物激活剂候选化合物,以三乙胺为缚酸剂,通过4-甲基-1,2,3-噻二唑-5-甲酰氯与酚类化合物在二氯甲烷中于室温下反应,制得一系列共20个4-甲基-1,2,3-噻二唑-5-甲酸芳酯化合物,其中9个化合物未见文献报道,所有化合物的结构均得到了核磁共振氢谱、红外光谱、高分辨质谱的表征和确认。选择化合物 2g 培养了单晶,利用X-射线单晶衍射确证了该类化合物的空间结构。杀菌活性测定结果表明:部分化合物在50 μ g/mL下具有显著的离体杀菌活性,其中化合物 2c,2n和2o 具有广谱的杀菌活性,其EC50值在3.46~23.30 μ g/mL之间。生物活性测定结果表明,部分化合物显示了较好的抗病毒活性,大部分化合物对烟草花叶病毒(TMV)具有较好的钝化效果, 2a,2c,2d,2e,2f,2g,2l,2o 具有较好的诱导烟草抗TMV的活性。     

新型N-芳基-2-((5-((4,6-二甲基嘧啶-2-基)硫甲基)-1,3,4-噻二唑-2-基)硫)乙酰胺类化合物的合成及杀菌活性

为寻找新型杂环活性化合物,通过活性亚结构拼接,以硫脲和乙酰丙酮为起始原料合成4,6-二甲基嘧啶-2-硫醇,随后经酯化、肼化、环化和缩合反应,设计并采用微波辅助合成了10个新型N-芳基-2-（（5-（（4,6-二甲基嘧啶-2-基）硫甲基）-1,3,4-噻二唑-2-基）硫）乙酰胺类化合物,其结构通过核磁共振氢谱和碳谱、红外光谱、质谱及元素分析确认。初步生物活性测试结果表明,在50 mg/L下,大部分目标化合物对植物病原真菌具有一定的抑制活性,其中化合物8h对黄瓜炭疽病菌Colletotrichum orbiculare的抑制率达77.3%。     

2-[4-(对氟苯基)噻唑-2-基]-3-羟基-3-烃氧基丙烯腈的合成及杀菌活性

为了寻找生物活性良好的噻唑基丙烯腈类化合物,利用2-氰甲基-4-(对氟苯基)噻唑( 3 )与取代氯甲酸酯( 4 )在碱存在下反应,合成了15个未见文献报道的2- -3-羟基-3-烃氧基丙烯腈化合物( 5 ),其结构经核磁共振氢谱、质谱和元素分析表征。初步杀菌活性测试结果表明:所有化合物在试验浓度下均具有一定的抑菌活性,尤其对炭疽病菌Colletotrichum gossypii表现出较好的抑制活性,在质量浓度25 mg/L下,所有化合物的抑制率均在50%以上,其中化合物 5a、5e、5g、5k、5n和5o 的抑制率在80%以上。     

10种N-取代氨基香豆素的合成及生物活性

基于结构拼接思想,设计合成了10个N-取代氨基香豆素类化合物,并测定了其抑菌及除草活性。6-硝基香豆素经Fe/NH4Cl还原得6-氨基香豆素,再与不同醛缩合得Schiff碱,最后经硼氢化钠还原制得10个N-取代氨基香豆素类化合物(4a~4J),其中9个未见文献报道,其结构均经红外光谱、核磁共振氢谱和质谱确认。抑菌活性测试结果表明,所有化合物对苹果腐烂病菌Valsa mali、葡萄白腐病菌Coniothyrium diplodiella、棉花枯萎病菌Fusarium oxysporium和柑橘炭疽病菌Citrusanthrax bacteria均有一定抑制作用,其中 4e 的抑菌活性最强,对苹果腐烂病菌和柑橘炭疽病菌的EC50值分别为7.53和12.93 mg/L,对其余2种植物病原菌的EC50值均小于25 mg/L;化合物 4f 次之,对苹果腐烂病菌和葡萄白腐病菌的EC50值均约为11 mg/L。除草活性测试结果表明,除 4f 外,所有目标化合物均有一定除草作用,其中 4c 的活性最强,100 mg/L下对反枝苋Amaranthus retroflexus种子根、茎生长的抑制率均为99%。     

松油烯-4-醇对家蝇超氧化物歧化酶、过氧化氢酶及过氧化物酶的影响

以杀虫植物砂地柏Sabina vulgaris Ant.精油中主要杀虫成分——松油烯-4-醇点滴处理家蝇成虫后,测定其兴奋期、痉挛期、麻痹期及复苏期等4个中毒阶段试虫的超氧化物歧化酶(SOD)、过氧化氢酶(CAT)及过氧化物酶(POD)活性。结果表明:SOD被明显激活,各中毒阶段的酶比活力均较对照高,差异显著,且表现为先增高后下降的趋势;CAT先被抑制后被激活,在复苏期酶比活力为对照的1.19倍,其中兴奋期和复苏期酶比活力与对照差异显著,而痉挛期和麻痹期与对照无明显差异;POD被明显激活,各中毒阶段的酶比活力依次为对照的2.25、2.04、1.23和2.91倍,与对照差异极显著。上述结果表明,保护酶活性的变化与松油烯-4-醇的作用有密切关系,SOD活力增加可能是松油烯-4-醇的诱导反应,而中毒试虫的复苏可能与CAT和POD活力的变化有关。     

2-(4-芳基噻唑-2-基)-3-羟基丙烯腈类化合物的合成及其生物活性

为了寻找新的含2-噻唑基丙烯腈结构的先导化合物,利用2-(4-芳基噻唑-2-基)乙腈与酰氯在吡啶或氢化钠存在下反应,合成了9个2-(4-芳基噻唑-2-基)-3-羟基丙烯腈类化合物,其中8个为新化合物,利用1H NMR、MS和元素分析对其结构进行了表征。初步的生物活性测定结果表明,部分化合物在供试浓度下具有一定的杀虫、杀菌活性,其中化合物 5f 在100 mg/L下对棉花枯萎病菌Fusarium oxysporium的抑制率超过90%,化合物 5e 在250 mg/L下对蚕豆蚜Aphis fabae的致死率达95%。毒力测定结果表明, 5e 对蚕豆蚜的活性优于对照化合物2- -3-羟基-3- 丙烯腈( 6 )。     

砂地柏果实油杀虫成分松油烯-4-醇的超临界流体萃取

采用超临界流体萃取-气相色谱法,以砂地柏Sabina vulgaris Ant.果实油主要杀虫活性成分松油烯-4-醇的萃取率为评价指标,提出了砂地柏果实油中松油烯-4-醇的超临界流体萃取较优工艺条件为:萃取物料粒径0.85 mm(20目),静态萃取10 min,萃取温度45℃,压力34.47 Mpa,流体CO2总流量30 mL/g。采用该法对砂地柏果实油中松油烯-4-醇的萃取率达2.72 mg/g,明显高于水蒸气蒸馏法(萃取率为2.00 mg/g),并具有快速、简便、精确、无毒、经济等优点。     

芳甲酰氨基环丙酸的合成及其生物活性

以与脱落酸具有相同受体的化合物pyrabactin为先导,用1-氨基环丙酸替代2-氨甲基吡啶,设计合成了17个具有脱落酸功能的类似物(芳甲酰氨基环丙酸),其中13个为未经文献报道的新化合物。其结构均经过核磁共振氢谱、红外光谱和高分辨质谱(HRMS)确证。初步生物活性测试结果表明,大部分目标化合物表现出一定的延缓种子萌发活性,其中化合物 B4、B8和B11在5000μmol/L时的活性优于脱落酸。     

Fumigant and contact toxicity of Myrtaceae plant essential oils and blends of their constituents against adults of German cockroach (Blattella germanica) and their acetylcholinesterase inhibitory activity

Fumigant and contact toxicities of 11 Myrtaceae plant essential oils and their constituents against adult male and female Blattella germanica were evaluated. Of 11 Myrtaceae plant essential oils, Eucalyptus polybractea, Eucalyptussmithii, Eucalyptusradiata, Eucalyptusdives, Eucalyptusglobulus, and Melaleuca uncinata, showed 100% fumigant toxicity against adult male German cockroaches at a concentration of 7.5 mg/liter air concentration. In contact toxicity tests, E. polybractea, E. smithii, E. radiata, E. dives, E. globulus, Melaleucadissitiflora, and M. uncinata produced strong insecticidal activity against adult male and female German cockroaches. Of the essential oil constituents, terpinolene, α-terpinene, and terpinen-4-ol demonstrated strong fumigant toxicity against adult male and female B. germanica. Eugenol, isoeugenol, methyl eugenol, and terpinen-4-ol showed strong contact toxicity against adult male B. germanica. The toxicity of the constituent blends identified from M. dissitiflora essential oils indicated that terpinen-4-ol were major contributor to the fumigant activity or contact toxicity of the artificial blend. Only isoeugenol exhibited inhibition activity against male acetylcholinesterase. IC₅₀ values of isoeugenol were 0.22 mg/mL against male acetylcholinesterase.     

Synthesis and insecticidal activities of novel derivatives of podophyllotoxin: Part XII

In order to find the biorational pesticides, eight novel 4β-substituted phenoxyaniline derivatives of podophyllotoxin have been synthesized with significant stereoselectivity and improved yields by employing the BF₃·Et₂O/NaI reagent system and evaluated for their antifeedant effect against 5th instar larvae of Pieris rapae and effect on the development of 5th instar larvae of P. rapae as well as for insecticidal activity against P. rapae. The antifeedant activities showed that these compounds exhibited less potent than podophyllotoxin. Though these derivatives showed less potent antifeedant activities than podophyllotoxin, they acted as growth development inhibitor to 5th instar larvae of P. rapae, which were found that the animals treated with podophyllotoxin and its derivatives showed moulting disturbances and/or deformities. Also, the insecticidal activity results show that all of these derivatives of PPT showed delayed insecticidal activity, which differs from traditional neurotoxic insecticides. Among them, compounds possessing a 4β-phenoxyaniline moiety substituted (CO₂C₂H₅, Cl and OH) at para position exhibited greater insecticidal activity against P. rapae than podophyllotoxin.     

20-(S)-喜树碱7-C-取代衍生物的合成及杀松材线虫活性研究

为研究喜树碱(CPT)类化合物的杀线虫活性,以喜树碱为原料,经烷基化、氧化、酯化等步骤合成了13个7-C-取代的20-(S)-喜树碱衍生物,其中化合物 14 未见文献报道,所有衍生物的结构经红外光谱(FT-IR)、核磁共振氢谱(1H NMR)和液-质联用(LC-MS)等分析手段进行了表征。采用浸渍法测定了化合物对松材线虫Bursaphelenchus xylophilus的毒杀活性。结果表明:与母体化合物喜树碱相比,7-C-取代的20-(S)-喜树碱衍生物具有更强的杀线虫活性,其中化合物7-苄基喜树碱、7-甲酰基喜树碱、7-苯甲酰氧甲基喜树碱在24 h的致死中浓度(LC50值)分别为2.28、2.21和1.37 mg/L,明显高于母体化合物喜树碱的LC50值12.18 mg /L。     

2-氧代和2-羟基环烷基磺酰胺对14种病原真菌的杀菌活性

为了研究2-氧代和2-羟基环烷基磺酰胺类化合物的杀菌谱,选择N-(2-三氟甲基-4-氯苯基)-2-氧代和2-羟基环戊、己、庚、辛、十二烷基磺酰胺(A1～A5和B1～B5)共10个化合物,采用菌丝生长速率法测试了其对14种病原真菌的杀菌活性,并进行了初步的构效关系分析。在质量浓度50 mg/L下,2-氧代环庚、环辛烷基衍生物(A3、A4)和2-羟基环庚、环辛烷基衍生物(B3、B4)的杀菌谱接近或宽于对照药剂百菌清。精密毒力测定结果表明,化合物A3和B3对小麦赤霉病菌Gibberella zeae (Schw.) Petch、棉花黄萎病菌Verticillium dahliae等8种病原菌的EC50值均在20 mg/L以内。2-氧代和2-羟基对该类化合物杀菌活性的影响基本一致,7、8员环化合物的活性明显高于5、6员环和12员环化合物。     

五株土壤细菌所产抑菌挥发性物质的生物活性评估及其应用

为研究土壤细菌所产生的抑菌挥发性物质的生物活性及应用潜力,运用固相微萃取-气相色谱-质谱联用技术对5株细菌菌株所产生的活性挥发物进行提取和鉴定,在密封盘内,通过相对标准纯品对鉴定出的各主要化合物的抑菌活性进行确证,并分别通过土壤处理和直接熏蒸处理的方式调查这些活性挥发物对黄瓜菌核病Sclerotinia sclerrotium和白粉病Sphaerotheca fuliginea的温室生防效果。 结果表明, 从5株细菌的TSB-YE培养物及TSB-YE培养基对照分别测定出21~31 个和12个化合物,包括烷烃、醛、醇、酮、脂肪酸、胺、肟、酚及杂环类化合物;糠醛、苯甲醛、1-辛醇、 1-辛烯-3-醇和3,7-二甲基-1,6-二辛烯-3-醇,2-乙基-1-己醇在0.01g的处理量下便能够完全抑制菌核病菌S.sclerotiorum的生长;灭菌土与细菌混合对菌核病的防效为28.57%~71.43%,高于只进行底部处理的防效,并且对黄瓜幼苗有促生作用;直接熏蒸使用时,挥发物能够较明显地降低被熏蒸幼苗白粉病的发生程度。     

Involvement of lipoxygenase,lipoxygenase pathway volatiles,and lipid peroxidation during the hypersensitive reaction of pepper leaves to Xanthomonas campestris pv. vesicatoria

Lipoxygenase activity and protein, production of lipid-derived volatiles, and lipid peroxidation levels were determined in pepper (Capsicum annuum L., cv. Early Calwonder-10R) leaves during the hypersensitive reaction induced by avirulent race 2 of Xanthomonas campestris pv. vesicatoria. Lipoxygenase activity increased during the collapse phase of the hypersensitive reaction (8 to 12 h after inoculation), and an increase in electrolyte leakage occurred. However, Western blot analysis revealed that lipoxygenase proteins decreased during the same period. When only one longitudinal half of a pepper leaf was inoculated with the avirulent bacterium race, a significant increase in lipoxygenase activity was observed in both inoculated and noninoculated leaf halves, 10 h after inoculation. In addition, lipoxygenase protein decreased in inoculated leaf halves, but remained unchanged in noninoculated ones. The evolution of some volatile compounds derived from the lipoxygenase pathway [(E,E)-2,4-hexadienal, 1-hexanol, 3-hexen-1-ol, 2,4-hexadienal and 2,4-eptadienal] and carotenoid degradation (α- and β-ionone) increased in the incompatible interaction during the collapse phase of the hypersensitive reaction. The level of the oxidative index (A₂₃₅/A₂₀₅) of leaf lipid extracts, determined to estimate lipid peroxidation, significantly increased in the advanced stage of the hypersensitive reaction. Furthermore, determination of the oxidative index in neutral lipid, glycolipid and phospholipid fractions showed that the oxidative index was significantly increased only in the glycolipid fraction. Lipoxygenase activity and protein, electrolyte leakage, volatiles and lipid peroxidation were not changed in pepper leaves inoculated with the virulent race 1 of X. campestris pv.vesicatoria during the time interval considered (2–12 h after inoculations). The hypothesis that a lipoxygenase with chloroplastic location is induced in the incompatible interaction, and which is responsible for the increase in lipid peroxidation is advanced.     

N-(3,5-二甲氧基-4-烷氧基苯乙基)扁桃酰胺类杀菌剂的设计合成及杀菌活性

以第一个扁桃酰胺类杀菌剂双炔酰菌胺为模板,在炔丙氧基的邻位引入第二个甲氧基,设计合成了15个未见文献报道的 N-(3,5-二甲氧基-4-烷氧基苯乙基)扁桃酰胺类化合物(8a～8o),其结构通过核磁共振氢谱和高分辨质谱确认。初步的离体和活体杀菌试验结果表明,化合物 8e、8h和8o 对辣椒疫霉 Phytophthora capsici 具有较好的杀菌活性,其中 8h和8o 在62.5 mg/L下对辣椒疫霉活体抑制率达100%。     

氨基甲酸-2-氯吡啶-5-甲酯化合物的合成与抑菌活性

以芳香硝基化合物、2-氯-5-吡啶甲醇和一氧化碳为原料,在Pd-Fe/TiO2催化下进行羰基化反应,合成了11个新型氨基甲酸-2-氯吡啶-5-甲酯化合物,其结构经 1H NMR和MS表征。初步抑菌活性测定结果表明:在50 mg/L下,大多数目标化合物对4种供试病原菌具有一定的抑制活性,其中化合物 3f (4-甲氧基苯基氨基甲酸-2-氯吡啶-5-甲酯、3h (2,4-二氯苯基氨基甲酸-2-氯吡啶-5-甲酯)和 3j (3,4-二氯苯基氨基甲酸-2-氯吡啶-5-甲酯)对小麦赤霉病菌Gibberella zeae的抑制率达77.3%以上, 3f 对苹果轮纹病菌Physalospora piricola的抑制率达82.5%,与对照药多菌灵接近;所有化合物在50 mg/L下对番茄灰霉病菌Botrytis cinerea的抑制活性均优于对照药多菌灵。