负载戊唑醇的壳聚糖纳米胶囊的制备与性能研究

以戊唑醇为囊芯,壳聚糖和甲基丙烯酸甲酯为囊壁,采用自组装的方法制备了壳聚糖戊唑醇纳米胶囊。采用动态光散射仪(DLS)和透射电镜(TEM)对其粒径和形貌进行了表征,纳米胶囊的平均粒径(D50)为220 nm,分布系数(PDI)为0.23;经高效液相色谱仪测定,纳米胶囊的载药量为21.8%,包覆率为85.7%,体外释放192 h的释药率为65.97%。用带毒培养基法测试了其对3种木竹材霉菌的抑制性能。结果表明,与相同质量浓度(48.2 mg/L)的戊唑醇乙酸乙酯溶液相比,载戊唑醇纳米胶囊处理前20 d抑菌效果较低,但随着时间的延长仍能保持较高的抑菌活性,药剂处理40 d时对木霉、青霉、黑曲霉菌的抑菌率分别仍达70.6%、66.4%和89.1%。研究结果可为纳米胶囊木竹材防霉剂的开发奠定基础。     

A protocol for evaluation of the role of disinfectants in limiting pathogens and weed moulds in commercial mushroom production

In vitro and in vivo evaluations of the effects of three commercial disinfectants on isolates of Trichoderma harzianum Rifai and Cladobotryum dendroides (Bull) W Gams & Hoozemans were combined in the development of methodologies for realistic assessment of disinfectant performance. 'Environ' and 'Purogene' incorporated into agar media at 50 mg AI litre-1 were effective in totally preventing the mycelial growth of T harzianum and C dendroides isolates, whereas with 'Sudol' a concentration of 500 mg AI litre-1 was required. Evaluation of a model in vivo system was combined with observations on the fungicidal effects of disinfectants. Spore suspensions of T harzianum (Th1), T harzianum (Th2) and C dendroides prepared from culture washings with sterilised distilled water were used as contaminating inoculum. Environ, Sudol and Purogene in aqueous solutions at 1000 mg AI litre-1 were sprayed onto these building structure surfaces before or after artificial contamination with spore suspensions. Re-isolation from surfaces was carried out using agar swabs, which were prepared in visking tubing, applied to treated surfaces and incubated at 25 degrees C for 24, 48, 72 or 96 h. Environ and Purogene were more effective than Sudol in limiting the recovery of Trichoderma spp and C dendroides. All three disinfectants applied 12 h after artificial contamination onto wood, concrete or glazed surfaces were able to reduce the recovery of these isolates more effectively than when they were applied 12 h before artificial contamination. Greater persistence of contamination was noted on the rougher surfaces (wood and concrete) than on the smoother glazed surface. It was concluded in this in vivo evaluation that, in many cases, the protection achieved by the physical nature of the smooth glazed tile surfaces was equivalent to that available from the application of disinfectants, thus highlighting the attention needed to the nature of building surfaces in the structures used in the mushroom industry. The artificial contamination and re-isolation techniques allowed significant comparison between disinfectant materials, timings and surface types. In the in vivo experiments using a single standardised test concentration, the relative fungicidal effects of the disinfectants, which varied in the complexity of their active ingredients, were better discriminated than the effects observed in vitro, although the general trend was similar.     

Development of novel pesticides based on phytoalexins: Part 2. Quantitative structure-activity relationships of 2-heteroaryl-4-chromanone derivatives

Phytoalexins are low-molecular-weight chemicals that immune systems of plants produce and accumulate in response to infections, especially those of fungal origin. Although their content is not high in plants, yet they have shown unique fungicidal activity and played an important role in the defence system of plants. In searching for novel environmentally benign fungicides with high activity, the structures of flavanone derivatives, one of the most important phytoalexins groups, have been modified via bioisosteric substitution and a series of 2-heteroaryl-4-chromanones were designed and synthesized. They showed good fungicidal activities against rice blast disease, Pyricularia grisea (Sacc). Their IC50 values were tested in vitro and the relationship between structure and fungicidal activity was analyzed quantitatively using a Hansch-Fujita approach. The results showed that hydrophobicity was very important for fungicidal activity and there is apparently an optimum hydrophobic property for the molecules at a log Pow value of about 2.7. In addition, the results indicated that electronic effects played an important role in binding with the receptor and that the C=O group was probably a electron-accepting site. The quantitative structure-retention correlative equation of the title compounds was also established.     

菊科植物的杀菌活性及其活性成分(Ⅱ)

本文对菊科10个属:紫松果菊属(Echinacea)、醴肠属(Eclipta)、飞蓬属(Erigeron)、泽兰属(Eupatorium)、鼠曲草属(Gnaphalium)、堆心菊属(Helenium)、蜡菊属(Helichrysum)、旋复花属(Inula)、假泽兰属(Mikania)和银胶菊属(Parthenium)中具有杀菌活性的植物进行了综述,为进一步将菊科植物资源应用于植物性杀菌剂研究和开发利用提供理论参考。     

The chemistry and biological activity of a new class of azole fungicides: 1-amino-1,2,4-triazoles

The fungicidal activity of a novel class of triazole compounds in which the 1-position of the azole nucleus is bonded to a nitrogen atom was investigated. Such 1-amino-1,2,4-triazoles are amenable to great structural variation which allows the elucidation of the requirements for biological activity. As in most other triazole fungicides, the basic structural requirement for activity is a two-atom bridge connecting the azole nucleus to a hydrophobic group, typically an aromatic ring. The synthesis and optimization of fungicidal activity of this class of triazole fungicide are discussed.     

Synthesis and fungicidal activity of 1,4-dithiino[2,3-b]quinoxaline-2,3-dicarbonitriles

A series of eleven 1,4-dithiino[2,3-b]quinoxaline-2,3-dicarbonitriles was prepared by reaction of 2,3-dichloroquinoxalines with disodium (2)-2,3-dimercapto-2-butenedinitrile in N,N-dimethylformamide. These products were tested for in-vitro fungicidal activity by a Minimum Inhibitory Concentration (MIC) method. Several of these compounds showed broad-spectrum fungicidal activity. The activity exhibited by these compounds was greatly dependent upon the substituents of the quinoxaline ring, with the nitro-substituted derivatives showing the highest levels of antifungal activity. None of the compounds prepared, however, showed fungicidal activity comparable to that of the commercial fungicides screened.     

杀菌剂生物测定技术的发展

概述了杀菌剂生物测定的发展历史,探讨了离体、活体和组织筛选的常规生物测定技术,以及高通量筛选方法,同时从多个角度阐述了杀菌剂生物测定技术的发展趋势。     

含嘧啶硫醚的嗜球果伞素类化合物的设计、合成及杀菌活性

为了发现和开发新的杀菌化合物,以嘧菌酯为先导,通过活性亚结构拼接等手段,设计并合成了22个新化合物,通过核磁共振氢谱、碳谱及高分辨质谱等手段对其结构进行了表征.生物活性测试结果表明,部分化合物对黄瓜白粉病菌表现出较好的杀菌活性,其中化合物7b在50 mg/L下对黄瓜白粉病菌的抑制率为85％.田间试验结果显示,在有效成分...     

含1,3,4-噻(噁)二唑吩嗪-1-甲酰胺类衍生物的合成与杀菌活性

对广泛存在于链霉菌和铜绿假单胞菌中的一种天然活性物质——申嗪霉素进行了结构修饰,合成了一系列高活性的含1,3,4-噻(噁)二唑的申嗪霉素衍生物 I ₁ ~ I ₂₈ 。杀菌活性测定结果表明:所有目标化合物对禾谷镰刀菌具有较好的杀菌活性,均明显优于母体申嗪霉素。离体杀菌活性测定结果显示,化合物 I ₈ (EC₅₀ = 33.25 μg/mL)和化合物 I ₂₂ (EC₅₀ = 46.52 μg/mL)对禾谷镰刀菌的杀菌活性是申嗪霉素 (EC₅₀ = 128.54 μg/mL)的3~4倍。活体杀菌活性显示,在500 μg/mL质量浓度下,化合物 I ₈ (58.69%)和化合物 I ₂₂ (55.37%)对禾谷镰刀菌的抑制率是申嗪霉素 (25.14%) 的两倍。构效关系分析结果表明,在苯环上引入吸电子基团对化合物的活性不利;而引入给电子基团则有利于提高其杀菌活性。同时,同一取代基在苯环上的取代位置依据活性的高低排列顺序为:邻位>对位>间位。这些结果可用于指导该类化合物的进一步结构改造。     

杀菌剂生物测定技术的发展

概述了杀菌剂生物测定的发展历史,探讨了离体、活体和组织筛选的常规生物测定技术,以及高通量筛选方法,同时从多个角度阐述了杀菌剂生物测定技术的发展趋势。     

Fungicidal β-methoxyacrylates: From natural products to novel synthetic agricultural fungicides

The strobilurins and oudemansins are natural β-methoxyacrylates which inhibit mitochondrial respiration and, as a result, have fungicidal activity. A knowledge of the structures (configuration and conformation) and properties of these compounds has allowed the preparation of analogues in which both fungicidal activity and stability have been improved.     

Diastereoisomers and enantiomers of paclobutrazol: Their preparation and biological activity

Paclobutrazol is a highly active plant growth regulator with very good fungicidal activity. Aspects of the synthesis of paclobutrazol and its diastereoisomer are discussed, the resolution of paclobutrazol into its two enantiomers is described. It has been shown for the first time that it is possible to separate the plant growth regulatory activity from the fungicidal activity by resolution. Computer graphic studies are also included.     

5种甾醇生物合成抑制剂类(SBIs)抗真菌药物对9种植物病原真菌的活性筛选

为了寻找高效、低毒以及环境友好型的农药先导化合物,通过菌丝生长速率法测定了5种甾醇生物合成抑制剂类(SBIs)抗真菌药物(益康唑、氟康唑、伏立康唑、酮康唑和咪康唑)对7种植物病原菌的抑制效果,选择其中活性较高的药物进行了防治小麦白粉病和水稻纹枯病的盆栽试验及防治小麦条锈病和水稻纹枯病的田间药效试验。室内毒力测定结果表明:伏立康唑对供试的7种植物病原真菌的杀菌活性最高,其EC50值均低于0.349 mg/L,咪康唑对小麦赤霉病菌、梨黑斑病菌、西瓜枯萎病菌和香樟炭疽病菌,益康唑对梨黑斑病菌和西瓜枯萎病菌,以及酮康唑对水稻稻瘟病菌均表现出较强的杀菌活性,且均高于对照药剂苯醚甲环唑。盆栽试验结果显示:在药剂质量浓度为37.5 mg/L时,伏立康唑和氟康唑对小麦白粉病的防治效果分别为98.26%和89.11%,明显高于商品化杀菌剂三唑醇;在质量浓度为150 mg/L时,益康唑对水稻纹枯病的防治效果最好,为86.14%。田间试验结果表明:在有效剂量为240 g/hm^2时,氟康唑对小麦条锈病的防效为98.42%,益康唑对水稻纹枯病的防效为75.21%。研究结果表明,临床上的抗真菌药物氟康唑、伏立康唑和益康唑对植物病原真菌也具有很高的活性,可望作为农用杀菌剂的先导化合物进一步研究。     

Rationally Designed Guanidine and Amidine Fungicides

A previous investigation established that compounds containing a guanidinium or amidinium grouping are effective inhibitors of sterol Δ⁸–Δ⁷ isomerase and/or Δ¹⁴ reductase activity in plant pathogenic fungi. A binding model for known fungicidal inhibitors of this enzyme has now been used to rationally design further guanidinium or amidinium inhibitors. Three novel classes of chemistry were investigated. The results of biochemical testing against ergosterol biosynthesis in Ustilago maydis (DC) Corda and of in-vivo testing for fungicidal activity against Erysiphe graminis DC f. sp. hordei Marchal (powdery mildew of barley), do much to support the binding model, and compounds with significant fungicidal activity have been found. © 1997 SCI.     

N-取代苯基-1-(2,4-二氟苯基)-2-(1H-1,2,4-三唑-1-基)乙基氨基甲酸酯的合成及生物活性

为了寻找高活性的三唑类苯基氨基甲酸酯衍生物,以 1,2,4-三氮唑、2-氯-2,4-二氟苯乙酮为原料,采用活性亚结构拼接的策略,设计并合成了18个未见文献报道的N-取代苯基-1-(2,4-二氟苯基)-2-(1H-1,2,4-三唑-1-基)乙基氨基甲酸酯衍生物 6a ~ 6r 。其结构均通过 1H NMR、13C NMR和高分辨质谱（HRMS）的确证。抑菌活性测定结果显示:在100 μmol/L下,化合物 6m 对6种供试真菌具有良好的抑制作用,抑制率均达到50%以上。化合物 6p 对油菜菌核病菌Sclerotinia sclerotiorum的EC₅₀值为7.1 μmol/L,抑菌活性高于对照药剂烯唑醇（EC₅₀值9.1 μmol/L）。杀螨活性测定结果显示,在150 μmol/L时,化合物 6h 、 6k 和 6o 在48 h时对朱砂叶螨Tetranychus cinnabarinus的致死率分别为67.7%、74.9%和57.5%,杀螨活性低于对照药剂阿维菌素B1a(致死率100%)。本研究所合成的化合物 6o 兼具一定杀菌和杀螨活性,可为新型三唑类杀菌杀螨化合物的设计与研究提供参考。     

苦皮藤假种皮中的杀菌活性成分研究

用 5种溶剂对苦皮藤假种皮进行了系统提取 ,在灵敏的活性追踪指导下 ,从25%乙醇提取物中分离、鉴定了 3个具有杀菌活性的化合物 :麝香草酚、多羟基二氢沉香呋喃和间苯二酚 ,它们抑制玉米小斑病菌 Bip olaris maydis孢子萌发的 EC50 分别为 22 .27、53.32、169.29mg/L。其中麝香草酚为首次在卫矛科植物中分离得到 ,多羟基二氢沉香呋喃为首次在苦皮藤中分离得到。     

Triazolines VII. Results of screening l,5-diaryl-Δ2-l,2,3-triazolines for pesticidal properties

Twenty-one l,5-diaryl-δ2-l,2,3-triazolines were screened for the first time for pesticidal properties—insecticidal, fungicidal, bactericidal and virucidal. Five of the compounds showed some fungicidal activity, and 13 exhibited low level insecticidal activity, mostly toward the Mexican bean beetle.     

含氟2-氧代环己基磺酰胺的合成及杀菌活性

以环己酮为原料,经磺酰化、碱化后得到2-氧代环己基磺酸钾盐,再经生成酰氯后与胺反应得到9个新的标题化合物,其结构经1H NMR、13C NMR和元素分析确证。初步的生物测定结果表明,部分化合物具有一定的杀菌活性,其中 3e 对棉花立枯病菌Rhizoctonia solani和黄瓜灰霉病菌Botrytis cinerea、 3h和3i 对黄瓜灰霉病菌和油菜菌核病菌Sclerotinia sclerotiorum有较好的活性,50 μ g/mL下的抑制率均在90％以上。     

β-Methoxyacrylates; synthesis of new types of strobilurin fungicides with extended side chains

A series of novel oxime ether β-methoxyacrylates have shown good fungicidal activity against a number of fungal pathogens. These were designed by introducing a one- or two-atom spacer group adjacent to the oxime ether group. Best fungicidal activity was obtained when an amino spacer group was used. ©1999 Society of Chemical Industry     

丁香菌酯(SYP-3375)的设计、合成及杀菌活性

以乙酰乙酸乙酯为起始原料,经烷基化、合环、缩合等反应制得新型化合物(E)-2-[2-(3-正丁基-4-甲基-2氧代-7-色烯基氧)甲基苯基]-3-甲氧基丙烯酸甲酯,即丁香菌酯(SYP-3375),其结构经核磁共振氢谱、红外光谱和元素分析确认。生物活性试验结果表明:丁香菌酯在温室盆栽条件下对黄瓜霜霉病和白粉病的防效均低于对照药剂;在田间小区试验中,丁香菌酯对黄瓜霜霉病在有效成分剂量100 g/hm2下的防治效果与对照药剂烯肟菌酯和嘧菌酯相当;对小麦白粉病在有效成分剂量50和200 g/hm2下的防效略低于对照药剂烯肟菌酯或与之相当。初步的毒性数据表明丁香菌酯属低毒化合物。