Insecticidal 2-hydroxy-3-alkyl-1,4-naphthoquinones: correlation of inhibition of ubiquinol cytochrome c oxidoreductase (complex III) with insecticidal activity

The insecticidal and in vitro activities of four homologous series of 2-hydroxy and acetoxy-3-substituted-1,4-naphthoquinones have been measured and correlated with their (Log) octanol/water partition coefficients (Log Ko/w). In vitro activity against mitochondrial complex III was only exhibited by 2-hydroxy-3-alkyl-1,4-naphthoquinones, indicating that the 2-acetoxy compounds act as proinsecticides. Good correlation was observed between in vivo activity against the two-spotted spider mite, Tetranychus urticae and inhibition of complex III isolated from blowfly flight muscle. Both hydroxy and acetoxy analogues of individual compounds exhibited similar levels of in vivo activity with optimum activity for analogues with Log Ko/w values of 7-8. In contrast, the acetoxy derivatives showed superior in vivo activity against the tobacco whitefly, Bemisia tabaci. Complex III isolated from whitefly was optimally inhibited by hydroxy analogues with lower Log Ko/w values (6.0-6.5) and was also more sensitive than the blowfly enzyme to all the compounds tested.     

核盘菌(Sclerotinia sclerotiorum (Lib.) de Bary)侵染抑制黄瓜光合作用的机理

 以津春四号黄瓜(Cucumis sativus L. ‘Jinchun 4’)为实验材料,通过同时测定黄瓜叶片叶绿素荧光快速诱导动力学曲线和对820 nm光的吸收曲线,以及过氧化氢含量和过氧化氢酶(CAT)活性的变化,研究了核盘菌(Sclerotinia sclerotiorum(Lib.)de Bary)侵染黄瓜叶片后,对光系统Ⅰ(PSⅠ)和光系统Ⅱ(PSⅡ)功能的影响,并分析了核盘菌侵染后,两个光系统之间的相互影响。结果表明,核盘菌侵染叶片后,叶片过氧化氢(H₂O₂)含量升高,膜脂过氧化的程度加剧,叶片放氧能力下降,快速叶绿素荧光诱导动力学曲线发生变化。核盘菌侵染严重伤害了PSⅡ供体侧(放氧复合体)、受体侧以及反应中心的活性,并且降低PSⅠ最大氧化还原能力(△I/Io)。核盘菌侵染黄瓜后,抑制了CAT的活性,导致过量活性氧的积累,直接伤害了光合机构PSⅠ和PSⅡ的功能;对PSⅠ的伤害抑制了PSⅡ电子向PSⅠ的传递,进一步加剧了PSⅡ的伤害程度,导致更多过剩激发能产生,造成恶性循环,这是核盘菌抑制黄瓜光合作用的主要原因。     

1,3,4(2H)-isoquinolinetrione herbicides: Novel redox mediators of photosystem I

A series of 1,3,4(2H)-isoquinolinetriones have been found to be fast-acting post-emergence herbicides, producing symptoms of desiccation. These redox-active compounds are very potent stimulators of the light-dependent consumption of oxygen at photosystem I in isolated chloroplasts. Pulse radiolysis studies on 2-ethyl-1,3,4(2H)-isoquinolinetrione have shown it to have free-radical properties which could enhance the generation of superoxide radicals in plants. Electrochemical studies further support a redox mediator mode of action for the series. The compounds were found to be unstable towards hydrolysis, and this was considered to be a major factor limiting the overall herbicidal effects. Other parameters, related to uptake and/or translocation, which may limit the full expression of the herbicidal activity of certain compounds, are discussed.     

Effect of phytoplasmal infection on photosystem II efficiency and thylakoid membrane protein changes in field grown apple (Malus pumila) leaves

We have studied the effect of the apple proliferation phytoplasmal infection on some features of the thylakoids from field grown apple (Malus pumila) leaves. Changes in photosynthetic pigments, soluble proteins, ribulose-1,5-bisphosphate carboxylase, nitrate reductase, photosynthetic activities and thylakoid membrane proteins were investigated. The level of total chlorophyll and carotenoids were reduced in phytoplasma-infected leaves. Similar results were also observed for soluble proteins and ribulose- 1,5-bisphosphate carboxylase activity. The in vivo nitrate reductase activity was significantly reduced in infected leaves. When various photosynthetic activities were followed in isolated thylakoids, phytoplasmal infection caused marked inhibition of whole chain and photosystem II activity while the inhibition of photosystem I activity was only marginal. The artificial exogenous electron donors, diphenyl carbazide and hydroxylamine significantly restored the loss of photosystem II activity in infected leaves. The same results were obtained when F_v/F_m was evaluated by chlorophyll fluorescence measurements. The marked loss of photosystem II activity in infected leaves could be due to the loss of 47, 33, 28–25, 23 and 17 kDa polypeptides. It is concluded that phytoplasmal infection inactivates the donor side of photosystem II. This conclusion was confirmed by immunological studies showing that the content of the 33 kDa protein of the water-splitting complex was diminished significantly in infected leaves.     

Synthesis and herbicidal activity of 3-substituted toxoflavin analogs

We investigated the synthesis and herbicidal activity of 23 toxoflavin analogs, 1a–w, in which aromatic rings (R) were introduced into the C-3 position. In paddy field conditions, 1k (R=2-CF₃–C₆H₄) and 1w (R=2-thienyl) showed excellent herbicidal activity. Under upland field conditions, we found that toxoflavin analogs 1a (R=C₆H₅), 1n (R=2-CH₃O–C₆H₄), and 1p (R=4-CH₃O–C₆H₄) exhibited wide herbicidal spectrum against Echinochloa crus-galli (L) var. crus-galli (ECHCG), Chenopodium album, and Amaranthus viridis (AMAVI). The analog with the 2-fluoro group on benzene ring 1b also showed high herbicidal activity against both ECHCG and AMAVI.     

几种天然蛋白原料水解物的除草活性初步研究

以鱼粉、肉骨粉、豆粕、菜籽粕及芡粉等几种天然蛋白原料为底物,以碱性蛋白酶为水解酶制备出天然蛋白原料的水解物,用培养皿生物分析法检测不同蛋白原料水解物在不同浓度(0.5、1、2、5 mg/mL)条件下对杂草野菊种子的生根抑制活性。结果表明:不同蛋白原料制备出的水解物对野菊种子萌发根系生长均有抑制作用,并且随着浓度增加其抑制活性增强,不同蛋白原料水解物的除草活性有显著性差异,其除草活性顺序为:鱼粉水解物>肉骨粉水解物>豆粕水解物>菜籽粕水解物>芡粉水解物,水解物的根抑制活性与原料的蛋白含量及其水解物的多肽含量成正相关性,作者推测,天然蛋白水解物中的多肽可能是植物种子萌发时根系生长抑制活性物质,但这种根抑制活性究竟是由于特异性多肽的化感作用还是植物种子萌发时对高氮胁迫反应有待进一步研究。     

Phytotoxicity of m-phenoxybenzamides: Inhibition of cell-free phytoene desaturation

Inhibition of carotenoid biosynthesis by herbicidal m-phenoxybenzamide derivatives has been investigated in a cell-free carotenogenic system from Aphanocapsa. Their target is the phytoenedesaturase reaction. Double-reciprocal plots of β-carotene biosynthesis (from ¹⁴C-labeled geranylgeranyl pyrophosphate) showed that 3-(2,5-dimethylphenoxy)-N-ethylbenzamide was a noncompetitive inhibitor of the phytoene-desaturase complex. The K_i value for cell-free inhibition of β-carotene formation was almost identical to the I₅₀ value of intact cells. Furthermore, the influence of certain substituents on herbicidal activity has been investigated. Inhibition increased with the length of the unbranched N-alkyl chains. In addition, substituents at the phenoxy group with higher lipophilicities showed greater inhibitory activities. The presence of a phenoxy or trifluoromethyl moiety at position 3 is essential.     

Novel 1,3,5-triazine derivatives with herbicidal activity

New fluoroalkyl-substituted 1,3,5-triazine derivatives were synthesized and screened for herbicidal activity using a greenhouse pot test. Surprisingly, a series of 2-alkyl-4-fluoroalkyl-6-aralkylamino-1,3,5-triazines e.g. 6-(4-bromobenzylamino)-2-methyl-4-trifluoromethyl-1,3,5-triazine was found to possess strong pre- and post-emergence herbicidal activities, although the conventional herbicidal 1,3,5-triazines generally should have a 2-substituted-4,6-diamino-1,3,5-triazine structure for herbicidal activity. Our compounds show strong Photosynthetic Electron Transport inhibitory activity (PI₅₀ c 7). Although their herbicidal effect is considered to be caused by a process similar to that for the conventional 1,3,5-triazine herbicide atrazine, they can control atrazine-resistant Chenopodium album effectively, and will thus form promising trial compounds for new triazine herbicide design.     

吡啶衍生物研究(X):2-仲丁氨基-5-(2-芳氧吡啶 -4-基)-1,3,4-噻二唑的合成及除草活性

为了研究2-仲丁氨基-5-(2-氯吡啶-4-基)-1,3,4-噻二唑(BCPT)的结构-活性关系和开发活性更高的新型除草剂,以BCPT为先导化合物,依据活性亚结构连接法,在吡啶环2-位上引入二芳醚类除草剂的典型结构单元——芳醚,设计并合成了一系列新的芳氧吡啶噻二唑类化合物,其结构经元素分析和1H NMR确证。初步除草活性测定结果表明,在500 mg/L剂量下,所有化合物的除草活性(抑制率0~45%)远低于先导化合物(抑制率72％~87%),说明吡啶环2-位上的氯原子可能对维持该类化合物的除草活性是必需的。     

三氟羧草醚类似物的合成及除草活性

以2,5-二羟基苯甲酸甲酯和三氟羧草醚为起始原料,设计合成了3个系列20个新的三氟羧草醚类似物,通过核磁共振氢谱、碳谱对其结构进行了表征。分别采用小杯法和室内盆栽法测定了目标化合物的除草活性。结果表明,化合物 III-02 [5-(2-氯-4-三氟甲基苯氧基)-2-硝基苯甲酸-(6-甲基苯并噻唑-2-基)酯]对单子叶杂草的除草活性明显高于对照药剂三氟羧草醚,其对稗草Echinochloa crusgalli和马唐Digitaria sanguinalis根茎生长的EC₅₀值分别为2.03、0.93 μg/mL和1.49、0.52 μg/mL;在有效成分100 g/hm2的施药剂量下,化合物 III-02 对单子叶杂草稗草、马唐及狗尾草Setaria viridis的防治效果均在85%以上,明显高于三氟羧草醚,对阔叶杂草马齿苋Portulaca oleracea、反枝苋Amaranthus retroflexus及苘麻Abutilon theophrasti的防治效果可达100%。初步构效关系表明,2-硝基苯甲酰衍生物的除草活性明显优于其2-甲氧基衍生物,三氟羧草醚苯甲酸酯衍生物对单子叶杂草的除草活性明显高于其苯甲酰胺衍生物。     

1,3,4(2H)‐Isoquinolinetriones: evaluation of amino‐substituted derivatives as redox mediator herbicides

Amino‐substituted derivatives of 2‐ethyl‐1,3,4(2H)‐isoquinolinetrione have been prepared with the aim of enhancing their hydrolytic stabilities relative to other isoquinolinetriones, and hence potentially improving their herbicidal effects. 5‐Amino‐2‐ethyl‐1,3,4(2H)‐isoquinolinetrione has been shown to be 12 and 8 times more stable towards hydrolysis than the isomeric 7‐ and 8‐amino derivatives, respectively, and 120 times more stable than 2‐ethyl‐1,3,4(2H)‐isoquinolinetrione itself. Pulse radiolysis studies have shown 5‐amino‐2‐ethyl‐1,3,4(2H)‐isoquinolinetrione to have free‐radical properties which could enhance the generation of superoxide radicals in plants. The compound is a potent stimulator of the light‐dependent consumption of oxygen at photosystem I in isolated chloroplasts and also shows high activity in isolated leaf discs. Evidence is presented which indicates that the rate of foliar uptake is a major factor affecting herbicidal activity for this compound. © 2000 Society of Chemical Industry     

棉籽壳中除草活性物质提取及鉴定

为了开发利用棉籽壳中的除草活性物质，分别以无水乙醇、正丁醇、石油醚和乙酸乙酯为溶剂，采用索氏提取法对棉籽壳中的活性物质进行了提取，并对各溶剂粗提物进行了除草活性测定。结果发现:用无水乙醇提取的粗提物对稗草生长的抑制活性最高，经气相色谱-质谱(GC-MS)联用分析，发现该粗提物中主要含有甘油、三环己基3-烯-6-辛酮、4-乙烯基-2-甲氧基苯酚、(邻甲基苯酚)-2-溴-2氯-乙酰酯、十四酸、十四酸乙酯、十六烷酸、辛酸异戊酯和亚油酸9种化合物。进一步的除草活性测定结果表明，亚油酸、辛酸异戊酯、4-乙烯基-2-甲氧基苯酚和(邻甲基苯酚)-2-溴-2氯-乙酰酯4种化合物对稗草表现出一定的除草活性，其中亚油酸活性最强，其IC₅₀值为14.5 mg/L。     

Synthesis and herbicidal activities of novel 3-(substituted benzyloxy or phenoxy)-6-methyl-4-(3-trifluoromethylphenyl)pyridazine derivatives

BACKGROUND: 4‐(3‐Trifluoromethylphenyl)pyridazine represents a new series of compounds with bleaching and herbicidal activities. RESULTS: A total of 43 novel 3‐(substituted benzyloxy or phenoxy)‐6‐methyl‐4‐(3‐trifluoromethylphenyl)pyridazine derivatives were synthesised, and their bleaching and herbicidal activities were evaluated through Spirodela polyrrhiza and greenhouse tests. Some compounds exhibited excellent herbicidal activities, even at a dose of 7.5 g ha^?1. CONCLUSION: The results showed that a substituted phenoxy group at the 3‐position of the pyridazine ring and the electron‐withdrawing group at the para ‐position on the benzene ring were essential for high herbicidal activity. Copyright © 2011 Society of Chemical Industry     

Mode of action of meturine

The effect of meturine on the light processes of photosynthesis was studied.Meturine is a herbicide for weed control in potato and cotton crops. It is a N-phenyl—N-hydroxy—N′-methylurea.The experiments were carried out on isolated pea and spinach chloroplasts.When examining photosystem I, reduced DPIP was used as an electron donor, whereas methyl-viologen served as an electron acceptor. When examining photosystem II, DPIP represented the electron acceptor.The obtained experimental results have pointed to the absence of the effect of meturine upon the photoreaction I.Unlike N-phenyl—N′, N′-dimethylureas (CMU, DCMU) meturine has been a very weak inhibitor of photoreaction II.The authors explain the photoreaction II inhibition of chloroplasts from plants treated with herbicidal doses of meturine by conversion of N-phenyl—N-hydroxy—N′-methylurea into Hill reaction inhibitor(s). N-Phenyl—N′-methylurea can be one of such meturine metabolites.Meturine herbicidal action is accounted for by meturine transformation into Hill reaction inhibitor(s) in the plant tissues.     

Structure-activity relationship of herbicides inhibiting ACh-induced contractions in a molluscan smooth muscle

Certain herbicides are known to influence the muscle function of molluscs. The penis-retractor muscle complex (PRM complex) of the edible snail, Helix pomatia, is a suitable test object for studying these side effects in smooth muscle, because sequential contractions can be induced in vitro by adding and removing acetylcholine (ACh). In the presence of herbicidal amides, carbamates, and ureas (concentration, 10^?4 mol/liter) the muscle tension was found to be reduced to a variable extent. In contrast, the relaxing effect of herbicidal phenoxycarbonic acids was weak. The inhibitory properties of the herbicides tested were correlated with the electron-withdrawing properties of certain substituents. These substituents are bound to an amino function. Their structure is either aromatic (amides, biscarbamates, carbamates, ureas), aliphatic (thiocarbamates), or cycloaliphatic (cycloat). The structure-activity relationship is comparable with that found for herbicidal activity in plants.     

Mode of action of new diethylamines in lycopene cyclase inhibition and in photosystem II turnover

The new bleaching herbicidal compound N,N‐diethyl‐N‐(2‐undecynyl)amine (NDUA) is identified here as an inhibitor of lycopene cyclase and is compared with the known cyclase inhibitors N,N‐diethyl‐N‐[2‐(4‐chlorophenylthio)ethyl]amine (CPTA) and N,N‐diethyl‐N‐[2‐(4‐methylphenoxy)ethyl]amine (MTPA). HPLC separation of chloroplast pigments shows lycopene accumulation in NDUA treated tissue. Variation in chain length of the undecynylamine moeity of NDUA from 7 to 21 C atoms reveals an optimum of 11 to 14 C atoms for herbicidal activity. A series of seven further analogues of NDUA and CPTA reveals the structural elements necessary for inhibition of lycopene cyclase. The effect of NDUA derivatives on photosynthesis has been studied in Chlamydomonas reinhardtii. Photosynthesis is highly sensitive, particularly towards the C14 and longer chain length analogues at nanomolar concentrations. It is shown that the breakdown of photosynthesis by NDUA is due to interference with the turnover of the D1 protein of the photosystem II reaction centre that requires the continous biosynthesis of the two reaction‐centre β‐carotene moieties in the reassembly phase. The D1 protein disappearance is most marked under strong light conditions. The depletion of photosystem II occurs before total pigment bleaching. This newly recognized mechanism in herbicidal activity is also the basis for the mode of action of other lycopene cyclase inhibitors as well as phytoene desaturase inhibitors. © 2001 Society of Chemical Industry     

含肟醚并取代异 NFDA1唑环的氨基甲酸酯类化合物的合成及生物活性

为寻找具有优异生物活性的氨基甲酸酯类化合物,根据活性亚结构拼接原理,将取代异 NFDA1 唑和肟醚基团引入多菌灵结构中,以取代苯甲醛 (1) 和2-氯苄胺(3) 为起始原料,经多步反应设计合成了10个未见文献报道的含肟醚并取代异 NFDA1 唑的氨基甲酸酯类化合物,其结构经 1H NMR 和 MS 确证。初步生物活性测定结果表明,部分目标化合物不仅具有一定的杀菌活性,同时还具有较好的除草活性。其中,活体盆栽试验结果表明,化合物11b对黄瓜霜霉病Pseudoperonospora cubensis 的相对防效为90%,对黄瓜白粉病Sphaerotheca fuliginea 的相对防效达95%,低于对照药剂多菌灵;除草活性皿测法表明,化合物11c和11j 200 mg/L下对靶标作物的根、茎抑制率均达80%以上,与对照药剂异丙酯草醚活性相当。盆栽法表明,150 g/hm2下,化合物11c和11j对繁缕Stellaria media苗前和苗后的抑制率均在70%以上,低于异丙酯草醚。此类化合物的构效关系有待进一步研究。     

牡丹皮提取物除草活性初步研究

为明确牡丹皮(Cortex Moutan Radicis)的除草活性并初步探索其活性成分分离条件,采用平皿法、土壤喷雾法及茎叶喷雾法测定了牡丹皮不同极性溶剂萃取物对反枝苋Amaranthus retroflexus和稗Echinochloa crus-galli的除草活性。平皿法测定结果显示,在1 mg/mL浓度下,牡丹皮正丁醇萃取物的除草活性最强,对反枝苋幼根和幼茎的抑制率分别为67.88%和65.71%,对稗草幼根和幼茎的抑制率分别为68.72%和71.32%;毒力测定结果表明,牡丹皮正丁醇萃取物对反枝苋幼根和幼茎的IC₅₀分别为12.28 mg/L和19.67 mg/L,对稗草幼根和幼茎的IC₅₀分别为43.35 mg/L和72.79 mg/L。土壤喷雾法和茎叶喷雾法测定结果显示,在5 mg/mL浓度下,牡丹皮正丁醇萃取物对反枝苋和稗草的鲜重抑制率最高,其中土壤喷雾法对反枝苋和稗草的鲜重抑制率分别为81.43%和83.18%;茎叶喷雾法对两种杂草的鲜重抑制率分别为80.83%和83.65%。由此可见,牡丹皮的除草活性成分主要集中在正丁醇...     

吡啶衍生物研究(IX):N-(1-甲氧羰基)乙基-N-[5-(2-氯吡啶-4-基)-1,3,4-噻二唑-2-基]酰胺的合成及除草活性

为了进一步研究前期发现的除草先导化合物2-仲丁氨基-5-(2-氯吡啶-4-基)-1，3，4-噻二唑(BCPT)的结构-活性关系并提高其除草活性，设计并合成了一系列N-(1-甲氧羰基)乙基-N-[5-(2-氯吡啶-4-基)-1，3，4-噻二唑-2-基]酰胺类化合物。其苗后除草活性测定结果表明，所有化合物的活性都远低于BCPT本身。说明BCPT可能具有与传统酰胺类除草剂不同的作用机制。     

荆条不同器官除草活性研究

为了明确荆条不同器官的除草活性,为进一步开展活性化合物的研究提供依据,采用琼脂混粉法于室内测定荆条对生菜、黄瓜、反枝苋、苘麻、小麦和稗草6种受体植物的除草活性。结果表明,在10 mg/mL的供试浓度下荆条不同器官粉末对6种植物幼苗均有明显的抑制作用,其中以花活性最高。进一步测定了花乙醇提取物及不同溶剂极性萃取物对6种植物幼苗生长的抑制作用,石油醚层和乙酸乙酯层的抑制活性较高,其中石油醚层对黄瓜幼根和乙酸乙酯层对稗草幼根的EC50分别为0.07、0.03 mg/mL,说明花含有较高的除草活性物质。