蓼二醛对蚜虫的拒食活性

辣蓼(Polygonum hydropiper L.)中的天然产物蓼二醛((-)-POLYGODIAL)具有很好的昆虫拒食活性。本文介绍了提取、分离的方法和含量测定。结果表明,我国辣蓼叶中含有蓼二醛约为0,08%。合成的蓼二醛在室内对空气、光和热的半衰期分别为34.6天、33.8天和15,6天。室内外生测结果表明,天然蓼二醛的乙醚提取物对蚜虫有很好的柜食活性。     

桂皮醛衍生物的合成及其对CVB3的作用

目的:合成桂皮醛衍生物,观测其对心肌细胞的毒性及抗CVB3病毒的作用.方法:化学合成6种桂皮醛衍生物,其中3种进行了红外、质谱等结构表征;MTT法检测被CVB3病毒感染和用桂皮醛衍生物治疗后的心肌细胞活性.结果:α-溴代对氨肉桂醛、α-溴代对甲基肉桂醛、对氯肉桂醛3种桂皮醛衍生物对心肌细胞的半教毒性浓度(TC50)分别为2151.28μ g·mL-1,1475.32μg·mL-1,22460.32μ g·mL-1;对CVB3病毒的半数抑制浓度(IC50)分别为178.94μg·mL-1、173.35μg·mL-1,6045.25μg·mL-1;对CVB3病毒的治疗指数(TI)分别为12.02,8.51,3.71.结论:桂皮醛3种衍生物具有直接抑制CVB3病毒作用,但对病毒的细胞合成和吸附无明显作用.     

核糖核酸一级结构微量分析方法的研究——Ⅳ.寡核糖核苷酸3′-端的显色标记微量测定法

本文报告用甲基橙为原料合成了甲基橙的两种衍生物:4-二甲氨基偶氮苯-4'-磺酰-甘氨酰肼(DABS-Gly-NHNH_2,Ⅰ)和4-二甲氨基偶氮苯-4'-磺酰肼(DABS-NHNH_2,Ⅱ),并用(Ⅰ)成功地标记了高碘酸氧化的核苷二醛。标记产物在聚酰胺薄板上分离得很好,其灵敏度达到10~(-9)～10~(-10)克分子,比紫外吸收法灵敏数十倍。我们用试剂(Ⅰ)标记测定了四种不同的寡核糖核苷酸的3'-端,用量为0.08～0.12A_(260)。     

萜类化合物对小菜蛾幼虫的拒食活性

采用叶碟浸液法测试从松节油合成的26个不同结构萜类化合物样品对小菜蛾Plutella xylostella(L.)4龄幼虫的拒食活性。结果显示,编号为2,4,8,13,27,31的6个化合物,即诺卜醇、诺卜丙基醚、内型异莰烷基甲醇丙酸酯、4-(1-甲基乙烯基)-1-环己烯-1-乙醇丙酸酯、羟基香茅醛丙酸酯、羟基香茅醛1,2-丙二醇缩醛具有较高的拒食活性。处理有效成分为0.01g/mL时,这6个化合物24h拒食率为70%～100%。其中2,4,8号3个化合物拒食活性最高,处理有效成分为0.01g/mL和0.001g/mL时,24h拒食率分别为98.33%,99.80%,100.00%和85.60%,83.90%,66.97%;并且持效性较好,72h拒食率分别为92.67%,89.97%,98.73%和63.20%,63.30%,45.93%。     

小莱蛾性诱素的合成及初步田间生测试验

<正> 日本玉置(Y.Tamaki,1977)等~*报道,小菜蛾Plutella xylostella(Linnaeus)性诱素的化学结构为顺-11-十六碳烯醛A和顺-11-十六碳烯醇醋酸酯B。我们于1977年,以1,10-癸二醇为原料,经下列反应合成了这二个化合物而制得产物A和B,其反应过程如下:     

衍生合成七种氮杂糖成分及其抑制α-葡萄糖苷酶构效关系分析

以白树(Suregada glomerulata)中分离得到的五个氮杂糖成分为底物,在其N上衍生合成,分析N上衍生基团对α-葡萄糖苷酶抑制活性的影响。分别合成了N-甲基化、N,N-二甲基化、N-丁基化和N-氧化衍生物,体外测试化合物的α-葡萄糖苷酶抑制活性。合成了7个未见文献报道的目标化合物,结构经1HNMR、13CNMR和MS确证。初步药理结果显示,所有衍生物均未见增强α-葡萄糖苷酶抑制活性。N-取代基对活性的影响较大;化合物5属于N,N-二取代衍生物,仍具有一定的α-葡萄糖苷酶抑制活性,值得进一步研究。     

杨小舟蛾雌蛾性信息素活性成分的鉴定

【目的】鉴定杨小舟蛾Micromelalopha sieversi雌蛾性信息素活性成分的结构信息。【方法】采用正己烷浸提的方法提取杨小舟蛾性成熟处女雌蛾性腺中的活性成分;利用气相色谱-触角电位联用(GC-EAD)技术对其活性成分进行定位;性腺提取物与4-甲基-1,2,4-三唑啉-3,5-二酮(MTAD)进行微量化学反应,获得衍生物;利用气相色谱-质谱联用(GC-MS)技术分别对性腺提取物及MTAD衍生物进行质谱特征离子分析。【结果】GC-EAD结果显示,杨小舟蛾雄蛾触角对雌蛾性信息素腺体提取物中的一种成分有较好的反应;GC-MS分析结果表明,能引起雄蛾触角电生理反应的成分为十八碳的不饱和醛;MTAD衍生物的GC-MS结果显示,该活性成分的两个双键分别位于碳链的13和15位。【结论】本研究鉴定出杨小舟蛾雌蛾性信息素活性成分的平面结构为13,15-十八碳二烯醛,但双键的立体构型有待合成标准化合物进一步鉴定。本研究为杨小舟蛾性信息素备选化合物的筛选提供了方向,为信息素的结构确证奠定了基础。     

桂皮醛衍生物的合成及其对CVB_3的作用

目的：合成桂皮醛衍生物,观测其对心肌细胞的毒性及抗CVB3病毒的作用。方法：化学合成6种桂皮醛衍生物,其中3种进行了红外、质谱等结构表征;MTT法检测被CVB3病毒感染和用桂皮醛衍生物治疗后的心肌细胞活性。结果：α-溴代对氯肉桂醛、α-溴代对甲基肉桂醛、对氯肉桂醛3种桂皮醛衍生物对心肌细胞的半数毒性浓度（TC50）分别为2151.28μg·mL-1,1475.32μg·mL-1,22460.32μg·mL-1;对CVB3病毒的半数抑制浓度（IC50）分别为178.94μg·mL-1、173.35μg·mL-1、6045.25μg·mL-1;对CVB3病毒的治疗指数（TI）分别为12.02,8.51,3.71。结论：桂皮醛3种衍生物具有直接抑制CVB3病毒作用,但对病毒的细胞合成和吸附无明显作用。     

核糖核酸一级结构微量分析方法的研究——Ⅰ.萤光试剂的制备和核苷二醛、5′-次甲基核苷二醛的萤光标记

本文报告了两种萤光试剂的制备方法并用一种萤光试剂标记了四种核苷二醛和四种5'-次甲基核苷二醛。萤光试剂Ⅰ,1-二甲氨基萘-5-磺酰-甘氨酰肼(DNS-Dly-NHNH_2)的制备方法:1-二甲氨基萘-5-磺酰氯(DNS-Cl)与甘氨酸乙酯(Gly-OC_2H_5)反应,得1-二甲氨基萘-5-磺酰-甘氮酸乙酯(DNS-Gly-OC_2H_5),DNS-Gly-OC_2H_5经肼解得DNS-Gly-NHNH_2。萤光试剂Ⅱ,1-二甲氨基萘-5-磺酰肼(DNS-NHNH_2)的制备方法:1-二甲氨基萘-5-磺酰氯直接肼解得1-二甲氨基萘-5-磺酰肼(DNS-NHNH_2)。DNS-Gly-NHNH_2与腺苷二醛,鸟苷二醛,胞苷二醛以及尿苷二醛反应,分别得到四种萤光标记的核苷腙:DNS-Gly-_(HO)A_R,DNS-Gly-_(RO)G_R,DNS-Gly-_(HO)C_R,以及DNS-Gly-_(HO)U_R。DNS-Gly-NHNH_2与5'-次甲基腺苷二醛,5'-次甲基鸟苷二醛,5'-次甲基胞苷二醛以及5'-次甲基尿苷二醛反应,分别得到四种萤光标记的5'-次甲基核苷腙:DNS-Gly-_(H_2)A_R,DNS-Gly-_(H_2)G_R,DNS-Gly-_(H_2)C_R以及DNS-Gly—_(H_2)U_R。     

核糖核酸一级结构微量分析方法的研究——Ⅰ.萤光试剂的制备和核苷二醛、5′-次甲基核苷二醛的萤光标记

本文报告了两种萤光试剂的制备方法并用一种萤光试剂标记了四种核苷二醛和四种5′-次甲基核苷二醛。萤光试剂Ⅰ,1-二甲氨基萘-5-磺酰-甘氨酰肼(DNS-Gly-NHNH_2)的制备方法:1-二甲氨基萘-5-磺酰氯(DNS-Cl)与甘氨酸乙酯(Gly-OC_2H_5)反应,得1-二甲氨基萘-5-磺酰-甘氨酸乙酯(DNS-Gly-OC_2H_5),DNS-Gly-OC_2H_5经肼解得DNS-Gly-NHNH_2。萤光试剂Ⅱ,1-二甲氨基萘-5-磺酰肼(DNs-NHNH_2)的制备方法:1-二甲氨基萘-5-磺酰氯直接肼解得1-二甲氨基萘-5-磺酰肼(DNs-NHNH_2)。DNs-GIy-NHNH_2与腺苷二醛,鸟苷二醛,胞苷二醛以及尿苷二醛反应,分别得到四种萤光标记的核苷腙:DNs-GlY-_(Ho)A_R,DNS-Gly-_(Ho)G_R,DNs-Gly-_(Ho)C_R,以及DNS-Gly-_(HO)U_R。DNS-Gly-NHNH_2与5′-次甲基腺苷二醛,5′-次甲基鸟苷二醛,5′-次甲基胞苷二醛以及5′-次甲基苷二醛反应,分别得到四种萤光标记的5′-次甲基核苷腙:DNS-Gly-_[H(?)]A_R,DNS-Gly-_[H(?)]G_R,DNS-Gly-_[H(?)]C_R 以及DNS-Gly-_[H(?)]U_R。     

Protective effects of polygodial and related compounds on ethanol-induced gastric mucosal lesions in rats: structural requirements and mode of action

The methanolic extract from the leaves of Tasmannia lanceolata was found to potently inhibit ethanol-induced gastric lesions in rats. Through bioassay-guided separation, three known sesquiterpenes, polygodial, polygodial 12 alpha-acetal, and polygodial 12 beta-acetal, and a new sesquiterpene, methyl isodrimeninol, were isolated as the active constituents. Among them, polygodial showed very potent gastroprotective effects (ED(50)=0.028 mg/kg, po). From the gastroprotective effects of various reduction and oxidation derivatives of polygodial, the dialdehyde or diacetal structure was found to be essential for the strong activity. Since the gastroprotection of polygodial was attenuated by pretreatment with indomethacin, N-ethylmaleimide, N(G)-nitro-L-arginine methyl ester and ruthenium red, endogenous prostaglandins, sulfhydryl compounds, nitric oxide and vanilloid receptors may be involved in the protective activity.     

Bioassay-guided isolation of three anthelmintic compounds from Warburgia ugandensis Sprague subspecies ugandensis, and the mechanism of action of polygodial

Parasitic helminths continue to pose problems in human and veterinary medicine, as well as in agriculture. Resistance to current anthelmintics has prompted the search for new drugs. Anthelmintic metabolites from medicinal plants could be good anthelmintic drug candidates. However, the compounds active against nematodes have not been identified in most medicinal plants with anthelmintic activity. In this study, we aimed to identify the active compounds against helminths in Warburgia ugandensis Sprague subspecies ugandensis (Canellaceae) and study the underlying mechanism of action. A bioassay-guided isolation of anthelmintic compounds from the plant was performed using a Caenorhabditis elegans (C. elegans) test model with a WMicrotracker instrument to monitor motility. Three active compounds were purified and identified by nuclear magnetic resonance and high resolution MS: warburganal (IC₅₀: 28.2?±?8.6?μM), polygodial (IC₅₀: 13.1?±?5.3?μM) and alpha-linolenic acid (ALA, IC₅₀: 70.1?±?17.5?μM). A checkerboard assay for warburganal and ALA as well as polygodial and ALA showed a fractional inhibitory concentration index of 0.41 and 0.37, respectively, suggesting that polygodial and ALA, as well as warburganal and ALA, have a synergistic effect against nematodes. A preliminary structure–activity relationship study for polygodial showed that the α,β-unsaturated 1,4-dialdehyde structural motif is essential for the potent activity. None of a panel of C. elegans mutant strains, resistant against major anthelmintic drug classes, showed significant resistance to polygodial, implying that polygodial may block C. elegans motility through a mechanism which differs from that of currently marketed drugs. Further measurements showed that polygodial inhibits mitochondrial ATP synthesis of C. elegans in a dose-dependent manner (IC₅₀: 1.8?±?1.0?μM). Therefore, we believe that the underlying mechanism of action of polygodial is probably inhibition of mitochondrial ATP synthesis. In conclusion, polygodial could be a promising anthelmintic drug candidate worth considering for further development.     

Multifunctional action of antifungal polygodial against Saccharomyces cerevisiae: involvement of pyrrole formation on cell surface in antifungal action

The antifungal activity of polygodial against Saccharomyces cerevisiae involves multifunctions. Polygodial first acts as a surface-active agent (surfactant) and then becomes involved in biochemical processes. The ability to form a pyrrole derivative with a primary amine group of phosphatidylethanolamine (PE) and phosphatidylserine (PS) in the outer monolayer of the plasma membrane is likely, in part, an initial step in the antifungal action of polygodial. In the lipid fraction derived from cells treated with polygodial, no PE and PS were detected, indicating a disturbance in the balance of the plasma membrane. The primary antifungal action of polygodial comes from its ability to act as a surfactant that nonspecifically disrupts the lipid–protein interface of integral proteins, denaturing their functioned conformation. Once polygodial enters the cytoplasm by destroying the membrane barrier, it reacts with l-cystein-containing cytoplasmic materials, such as a small molecule, glutathione, and a protein, alcohol dehydrogenase, to potentiate the antifungal action.     

Laboratory assessment of the antifouling potential of a soluble-matrix paint laced with the natural compound polygodial

Polygodial is a potent and selective inhibitor of ascidian metamorphosis that shows promise for controlling fouling by ascidians in bivalve aquaculture. The current study examined the potency of, and associated effects of seawater exposure on, a rosin-based soluble-matrix paint laced with 0.08–160?ng?polygodial?g^?1 wet paint matrix. Paint-coated surfaces were soaked in seawater for 0, 2, 4 or 12?weeks prior to screening for antifouling activity using a bioassay based on the nuisance ascidian Ciona savignyi Herdman. Mortality was greater (mean 50% lethal concentration: 5?±?2?ng?g^?1; mean 75% lethal concentration: 17?±?4?ng?g^?1) and metamorphosis was inhibited (mean 50% anti-metamorphic concentration: 2?±?0.4?ng?g^?1; mean 75% anti-metamorphic concentration: 15?±?10?ng?g^?1) in C. savignyi larvae exposed to polygodial-laced soluble-matrix paints, relative to control paints without polygodial. Soaking in seawater prior to testing reduced the efficacy of the formulation up to nearly 12-fold, but even after soaking for 12?weeks paints laced with polygodial at 160?ng?g^?1 wet paint matrix prevented ?90% of the larvae of C. savignyi from completing metamorphosis. The outcome of this experiment provides a positive first step in evaluating the suitability of polygodial-laced soluble-matrix paints for use in aquaculture.     

Biochemical Studies on “Bakanae” Fungus. Part 70–71. Synthesis of Substances related to Gibberellins

Several gibbane-10-carboxylic acids and esters, including methyl (±)-desoxogibberate and methyl (±))-desoxoepigibberate, were synthesized.     

Behavioural evidence for detection of the repellent polygodial by aphid antennal tip sensilla

Abstract. Close-up video was used to record responses of the aphid Myzus persicae (Sulzer) (Homoptera: Aphididae) to the plant-derived repellent polygodial. When 0.1% (±)-polygodial was painted onto one half of a Chinese cabbage leaf disc, and the other half treated with the ethanol solvent, apterous adult aphids avoided walking onto the polygodial-treated area during 15 min access periods. Similarly, when the rim of a small plastic Petri dish was treated with polygodial, aphids took significantly longer to walk off the base of the dish and onto the rim, compared with insects in solvent-treated control dishes. Analysis of video-recordings indicated that aphids were repelled following contact of antennal tips with the polygodial-treated areas of leaf or plastic. In contrast, aphids with both antennal tips surgically removed showed no apparent response to polygodial treatment of leaf or plastic surfaces. Aphids were placed between polygodial- and solvent-treated angled glass cover slips to enable unilateral presentation of polygodial on either the left or right side of the insects. Most aphids with antennae intact moved away from the polygodial-treated side, but removal of both antennal tips again negated the response. When the tip was removed from only one antenna, and the other remained intact, unilateral presentation caused a repellent response only if polygodial occurred on the same side as the intact antenna. Presentation of polygodial on both sides of aphids (bilaterally) caused no response if both antennal tips were intact or removed, but aphids with only one antennal tip removed were repelled from the side where the antenna remained intact. The results indicate that aphids detect polygodial upon contact with sensilla located on the antennal tips, and that the repellent response occurs as a negative chemotropotaxis following unilateral stimulation of these sensilla. Contact between the antennal tips and glass substrates was demonstrated using a fluorescent pigment.     

Effects of the antifeedant polygodial on plant penetration by aphids, assessed by video and electrical recording

Adult apterousMyzus persicae (Sulz.) discriminated within 2 min between mature Chinese cabbage (Brassica pekinensis L.) leaf halves treated with (±)-polygodial solution and solvent alone, and walked off leaf areas treated with polygodial faster than off the solvent-treated areas. However, when aphids were attached to a fine gold wire and stylet penetration of cabbage leaves was recorded electrically, polygodial treatment did not affect the number or duration of electrically-recorded penetrations, time taken to initiate a first penetration, or total penetration time. As the tethering of aphids causes behavioural restrictions which may negate the response to polygodial, indications of stylet penetration by freely-moving insects were sought. Simultaneous electrical recording and video monitoring showed that stylet penetration duration could be accurately inferred from antennal and body movements, enabling assessment of penetration times without attachment to the wire tether. When freely-movingM. persicae were video recorded during 15 min access to cabbage seedlings, polygodial treatment again had no apparent effect on stylet penetration. However, when aphids were presented with a choice of polygodial- and solvent-treated sides of floating mature cabbage leaf discs, video recordings revealed that the insects spent less time and made fewer penetrations on the polygodial-treated side. In addition to this rapid repellent effect, prolonged exposure to polygodial also produced behavioural changes. After being held for 24 h on polygodial-treated leaves or green paper prior to behavioural examination, aphids penetrated seedlings fewer times but for longer periods. The relevance of the results to virus transmission studies is discussed.     

Synthesis,Spectroscopic Analysis,and in Vitro/in Silico Biological Studies of Novel Piperidine Derivatives Heterocyclic Schiff-Mannich Base Compounds

In the present study, 3-substitued-4-(4-hydroxybenzylidenamino)-4,5-dihydro-1H-1,2,4-triazol-5-ones ( S1-8 ) were synthesized by treating 4-hydroxybenzaldehyde ( B ) with eight different 3-substitued-4-amino-4,5-dihydro-1H-1,2,4-triazole-5-ones ( T1-8 ) in acetic acid medium, separately. The synthesized Schiff bases ( S ) were reacted with formaldehyde and secondary amine such as 4-piperidinecarboxyamide to afford novel heterocyclic bases. 3-Substitued-4-(4-hydroxybenzylidenamino)-4,5-dihydro-1H-1,2,4-triazol-5-ones ( T ) were treated with 4-piperidinecarboxyamide in the presence of formaldehyde to synthesize eight new 1-(4-piperidinecarboxyamide-1-yl - methyl)-3-substitued-4-(4-hydroxybenzylidenamino)-4,5-dihydro-1H-1,2,4-triazol-5-ones ( M1-8 ). The structure characterization of compounds was carried out using ¹H-NMR, IR, HR-MS, and ¹³C-NMR spectroscopic methods. The inhibitory properties of the newly synthesized compounds were calculated against the acetylcholinesterase (AChE), butyrylcholinesterase (BChE), and glutathione S-transferase (GST) enzymes. Ki values were calculated in the range of 20.06±3.11–36.86±6.17 μM for GST, 17.87±2.91–30.53±4.25 μM for AChE, 9.08±0.69–20.02±2.88 μM for BChE, respectively, Besides, IC₅₀ values were also calculated. Best binding scores of -inhibitors against used enzymes were calculated as −12.095 kcal/mol, −12.775 kcal/mol, and −9.336 kcal/mol, respectively. While 5-oxo-triazole piperidine-4-carboxamide moieties have a critical role in the inhibition of AChE and GST enzymes, hydroxy benzyl moiety is important for BChE enzyme inhibition.     

Novel eugenol bearing oxypropanolamines: Synthesis,characterization, antibacterial,antidiabetic, and anticholinergic potentials

Five oxypropanol amine derivatives that four of them are novel have been synthesized with high yields and practical methods. in vitro antibacterial susceptibility of Acinetobacter baumannii, Pseudomonas aeruginosa, Escherichia coli and Staphylococcus aureus strains to synthesized substances were evaluated with agar well-diffusion method by comparison with commercially available drugs. Most of the bacteria were multidrug resistant. It was concluded that these compounds are much more effective than reference drugs. These eugenol bearing oxypropanolamine derivatives were also effective inhibitors against α-glycosidase, cytosolic carbonic anhydrase I and II isoforms (hCA I and II), and acetylcholinesterase (AChE) enzymes with K_i values in the range of 0.80 ± 0.24–3.52 ± 1.01 µM for hCA I, 1.08 ± 0.15–3.64 ± 0.92 µM for hCA II, 5.18 ± 0.84–12.46 ± 2.08 µM for α-glycosidase, and 11.33 ± 2.83–32.81 ± 9.73 µM for AChE, respectively.     

Dihydrozeatin: An improved synthesis and resolution of both isomers

(±)-Dihydrozeatin was synthesized in a 3-step synthesis by: (1) a Michael condensation of methyl methacrylate with nitromethane to give (±) - methyl 2 - methyl - 4 - nitrobutyrate, which was (2) reduced to (±) - 4 -amino - 2 - methylbutan - 1 - ol and (3) reaction of the aminoalcohol with 6-chloropurine. Hydrolysis of racemic nitroester gave (±) - 2 - methyl - 4 - nitrobutyric acid, which was resolved by means of (+) - and (-) -α -methylbenzylamine salts. Conversion of the salts to the corresponding methyl esters and subsequent reductions yielded optically active 4 - amino 2 - methylbutan - 1 - ols. Examination of the NMR spectra of the resolved methyl 2 - methyl - 4 - nitrobutyrates in the presence of a chiral shift reagent established their optical purities to be greater than 98%. The specific rotations at 589 nm of theS- (?) andR- (+)- dihydrozeatins derived from optically active butanols were appreciably lower than previously reported. Application of the Drude equation to ORD values from 320 to 589 nm verified the low 589 nm rotations of the dihydrozeatin enantiomers. The biological activities of (R), (S) and (R,S) dihydrozeatins in the betacyanin stimulation assay withAmaranthus parallel the activities found in other cytokinin bioassays.