胜红蓟地上部化感作用物的分离与鉴定

 胜红蓟(Ageratum conyzoides)是华南地区的重要杂草,具有显著的化感作用。本文利用色谱和波谱技术对胜红蓟地上部化感活性成分进行分离和化学结构鉴定,得到两个化感作用物质：胜红蓟素(6,7—二甲氧基—2,2—二甲基色烯)和5,22—二烯—3β—豆甾醇。对这两个作用物的化感作用研究表明：胜红蓟素对受体幼苗生长有抑制作用,500×10-6处理对稗草生长达到完全抑制,对萝卜的抑制率也高达90％。浓度降到25×10-6对稗草和萝卜幼苗生长仍具有显著的抑制作用。     

胜红蓟化感作用研究Ⅱ.主要化感物质的释放途径和活性

研究了南方重要杂草胜红蓟（Ａｇｅｒａｔｕｍｃｏｎｙｚｏｉｄｅｓ）挥发物质的化感作用．结果表明,胜红蓟鲜叶的挥发物质和挥发油对所有受试植物的幼苗生长有显著的抑制作用．用色谱法鉴定并分离了胜红蓟挥发油的主要成分早熟素Ⅰ和早熟素Ⅱ,两者分别占总量的３０．９３％和５１．６１％．胜红蓟水溶物中的早熟素Ⅰ和Ⅱ是从挥发物中而来,挥发是胜红蓟释放化感物质的主要途径．分离纯化的早熟素Ⅰ和Ⅱ的饱和水溶液对萝卜、番茄和黑麦草的幼苗生长均有显著的抑制作用,特别是早熟素Ⅱ具有强烈的化感作用,在２５μｇ·ｍｌ－１低浓度下,仍能抑制植物幼苗的生长,但早熟素Ⅰ和Ⅱ的混合溶液对植物的抑制作用并无显著增强,两者之间不存在协同作用．     

胜红蓟黄酮类物质对柑桔园主要病原菌的抑制作用

柑桔园引种杂草胜红蓟能有效地控制主要病害,研究发现,胜红蓟产生并释放到土壤中的黄桐类物质对疮痂病菌、炭疽病菌、白粉病菌和烟煤病菌等柑桔园主要病原真菌具有抑制活性,从胜红蓟植株中分离鉴定了10个黄酮物质,包括一个糖甙黄酮分子,但胜红蓟植株产生的大部分黄酮物质在土壤中会逐渐降解,只有3个黄酮分子能在柑梧园的土壤中累积并存在较长时间,而这3个黄酮物质对柑桔园主要病原真菌具有显著的抑制活性,其活性不仅超过胜红蓟释放的其化感物质,而且强于商业的杀菌剂多菌灵,表明胜红蓟产生和释放的黄酮物质在柑桔园病害控制中起着重要作用。     

胜红蓟化感作用研究I.水溶物的化感作用及其化感物质分离鉴定

研究了胜红蓟水溶物对植物的化感作用,结果表明,胜红蓟水溶物溶液浓度在０．２５ｇＦＷ．ｍｌ＾－１时对所有供试植物的萌发和幼苗生长均有显著的抑制作用,浓度降至０．１０ｇＦＷ．ｍｌ＾－１时其抑制作用基本消失,胜红蓟不同器官,不同生育期水溶物的化感作用是有差异的,特别是不同生境条件下生长的胜红蓟水物化感作用有显著差异,表明在恶劣生境下胜红蓟的化感作用更为强烈,对胜红蓟水溶物中的化感活性物质进行了分离和分子     

胜红蓟化感作用研究Ⅰ.水溶物的化感作用及其化感物质分离鉴定

研究了胜红蓟水溶物对植物的化感作用 .结果表明 ,胜红蓟水溶物溶液浓度在0 .2 5gFW·ml- 1 时对所有供试植物的萌发和幼苗生长均有显著的抑制作用 ,浓度降至0 .1 0 gFW·ml- 1 时其抑制作用基本消失 ;胜红蓟不同器官、不同生育期水溶物的化感作用是有差异的 ,特别是不同生境条件下生长的胜红蓟水溶物化感作用有显著差异 ,表明在恶劣生境下胜红蓟的化感作用更为强烈 .对胜红蓟水溶物中的化感活性物质进行分离和分子结构鉴定 ,得到早熟素Ⅰ、早熟素Ⅱ和 5,2 2 二烯 3β 豆甾醇 3个化感化合物 .     

胜红蓟化感作用研究Ⅵ.气象条件对胜红蓟化感作用的影响

在田间条件下 ,胜红蓟化感作用与光、温、水等气象要素显著相关 ,有利的光、温、水生长条件使得其化感作用减弱 ,反之增强 .春夏季温度和降水有利胜红蓟的生长 ,其化感作用减弱 ,而秋冬季温度和降水不利胜红蓟生长 ,其化感作用增强 .实验表明 ,30 0 μg·ml-1高浓度胜红蓟挥发油使受试植物不能生长 ,而6 0 μg·ml-1低浓度影响较小 ,在高温、低温和遮光等不利植物生长的条件下 ,低浓度的胜红蓟化感物质对受试植物的抑制效应显著增强 ,显示在不利的生长条件下 ,受试植物对胜红蓟化感物质的抵御能力减弱 .研究表明 ,在不利于胜红蓟及受试植物生长的气象条件下 ,胜红蓟化感作用增强 ,受试植物抵御化感物质的能力降低 ,使得胜红蓟群落中其它植物难以正常生长 ,相应地提高了胜红蓟在自然群落中的竞争优势 .化感作用和光、温、水、气象条件的共同作用是胜红蓟在自然群落中成为优势种群的重要原因之一 .     

胜红蓟化感作用研究 Ⅱ.主要化感物质的释放途径和活性

研究了南方重要杂草胜红蓟(Ageratumconyzoides)挥发物质的化感作用。结果表明,胜红蓟鲜叶的挥发物质和挥发油对所有受试植物的幼苗生长有显着的抑制作用。用色谱法鉴定并分离了胜红蓟挥发油的主要成分早熟素Ⅰ和早熟素Ⅱ,两者分别占总量的30.93%和51.61%.胜红蓟水溶物中的早熟素Ⅰ和Ⅱ是从挥发物中而来,挥发是胜红蓟释放化感物质的主要途径。分离纯化的早熟素Ⅰ和Ⅱ的饱和水溶液对萝卜、番茄和黑麦草的幼苗生长均有显着的抑制作用,特别是早熟素Ⅱ具有强烈的化感作用,在25μg·ml^-1低浓度下,仍能抑制植物幼苗的生长,但早熟素Ⅰ和Ⅱ的混合溶液对植物的抑制作用并无显着增强,两者之间不存在协同作用。     

胜红蓟化感作用研究V.挥发油对真菌、昆虫和植物的生物活性及其化学成份

胜红蓟挥发油对真菌、昆虫和植物均具有生物活性,对植物致病真菌和害虫的抑制活性尤其显著。挥发油及其主要成分胜红蓟素不仅具有杀虫活性,而且引起昆虫拒食和延迟蜕皮。用GC/MS详细分析了胜红蓟挥发油的化学成分,共鉴定了27个化合物,胜红蓟素及其衍生物,单萜和倍半萜类化合物是其主要成分。     

胜红蓟化感作用研究V．挥发油对真菌、昆虫和植物的生物活性及其化学成分

胜红蓟挥发油对真菌,昆虫和植物均具有生物活性,对植物致病真菌和害虫的抑制活性尤其显著,挥发油及其主要成分胜红蓟素不仅具有杀虫活性,而且引起昆虫拒食和延迟蜕皮。用GC／MS详细分析了胜红蓟挥发油的化学成分,共鉴定了27个化合物,且红蓟素及其衍生物,单萜和倍半萜类化合物是其主要成分。     

胜红蓟化感物质之间相互作用的研究

 通过柱层析从胜红蓟挥发油中分离出早熟素Ⅰ、早熟素Ⅱ、子丁香烯、3,3-二甲基-5-特丁基茚酮、红没药烯、乙酸葑醇酯等6种主要化感物质(占挥发油总量的97％),并研究了这些化感物质在挥发、淋溶(饱和水溶液)和土壤降解途径下对萝卜,番茄和绿豆幼苗的化感作用。结果表明：早熟素Ⅰ、早熟素Ⅱ、3,3-二甲基-5-特丁基茚酮及子丁香烯(挥发途径)虽有较强的化感活性,但均弱于挥发油的化感活性,而子丁香烯(淋溶途径),红没药烯和乙酸葑醇酯则基本无化感活性。但是,早熟素n和无活性的三个化感物质结合,则表现出强烈的化感活性,说明胜红蓟各化感物质之间存在着明显的协同作用。     

Simple 1,4-benzoquinones with antibacterial activity from stems and leaves of Gunnera perpensa

From the dichloromethane extract of the leaves and stems of Gunnera perpensa two new, simple 1,4-benzoquinones and a known benzopyran-6-ol were isolated. From the methanol extract phytol was obtained. The two benzoquinones, 2-methyl-6-(-3-methyl-2-butenyl)benzo-1,4-quinone (1) and 3-hydroxy-2-methyl-5-(3-methyl-2-butenyl)benzo-1,4-quinone (2) and the benzopyran, 6-hydroxy-8-methyl-2,2-dimethyl-2H-benzopyran (3) were examined for antimicrobial properties together with the crude stem, leaf and root extracts. Minimum inhibitory concentration (MIC) assays were used to quantify antimicrobial activity and the MIC values for the crude extracts of stems, roots and leaves ranged between 100 microg and >16 mg/ml against the eight microorganisms investigated. Compound 1 showed significant antimicrobial activity with the most sensitive organism being Staphylococcus epidermidis with an MIC of 9.8 microg/ml. For compound 2, no activity was noted. Compound 3 exhibited good activity against the yeasts Cryptococcus neoformans (75 microg/ml) and Candida albicans (37.5 microg/ml).     

Benzopyran Derivatives and an Aliphatic Compound from a Mangrove Endophytic Fungus Penicillium citrinum QJF‐22

Two new benzopyran derivatives, (2R,4S)‐5‐methoxy‐2‐methyl‐3,4‐dihydro‐2H‐1‐benzopyran‐4‐ol and (2S,4R,2′S,4′R)‐4,4′‐oxybis(5‐methoxy‐2‐methyl‐3,4‐dihydro‐2H‐1‐benzopyran), and a new aliphatic compound, (3E,5Z,8S,10E)‐8‐hydroxytrideca‐3,5,10,12‐tetraen‐2‐one, together with three known benzopyran derivatives, were obtained from a mangrove endophytic fungus Penicillium citrinum QJF‐22 collected in Hainan island. Their structures were determined by analysis of spectroscopic data and the relative configuration of (2R,4S)‐5‐methoxy‐2‐methyl‐3,4‐dihydro‐2H‐1‐benzopyran‐4‐ol was also confirmed by single‐crystal X‐ray diffraction. The absolute configurations of four compounds were established by comparison of ECD spectra to calculations. The configuration of (3E,5Z,8S,10E)‐8‐hydroxytrideca‐3,5,10,12‐tetraen‐2‐one was confirmed by comparison of optical value to the similar compound. The configurations of the compounds (2S,4S)‐5‐methoxy‐2‐methyl‐3,4‐dihydro‐2H‐1‐benzopyran‐4‐ol and (2R,4R)‐5‐methoxy‐2‐methyl‐3,4‐dihydro‐2H‐1‐benzopyran‐4‐ol were first determined. (3R,4S)‐3,4,8‐Trihydroxy‐3,4‐dihydronaphthalen‐1(2H)‐one exhibited moderate inhibitory effects on LPS‐induced NO production in RAW264.7 cells with IC₅₀ of 44.7 μM, and without cytotoxicity to RAW264.7 cells within 50 μM.     

Antioxidant activity in vitro of two aromatic compounds from Caesalpinia sappan L

Two antioxidant compounds were isolated from C. sappan L by multiple steps of column chromatography and thin layer chromatography in succession with superoxide scavenging assay as activity monitor. Structures of the two compounds were determined by spectroscopic methods as 1',4'-dihydro-spiro[benzofuran-3(2H),3'-[3H-2]benzopyran]-1',6',6',7'-tetrol (compound 1) and 3-[[4,5-dihydroxy-2(hydroxymethyl) phenyl]-methyl]-2,3-dihydro-3,6-benzofurandiol (compound 2). Characterization of antioxidant properties of these two compounds was done by determining the inhibitory effect on xanthine oxidase activity as well as scavenging effect on superoxide anion and hydroxyl radicals. Our results indicated that compounds 1 and 2 inhibited xanthine oxidase activity and scavenged superoxide anion and hydroxyl radicals. Compounds 1 and 2 possessed similar radical scavenging activities as ascorbic acid, and they were more effective than other well-known antioxidants such as alpha-tocopherol, beta-carotene, and BHT. As inhibitors of free radical formation, compounds 1 and 2 were more effective than all the other antioxidants tested. In conclusion, compounds 1 and 2 can be regarded as primary antioxidants with radical-scavenging and chain-breaking activities as well as secondary antioxidants with inhibitory effect on radical generation.     

Roles of in vitro plantlet age and growing period in the phenolic constituent yields of acclimatized Hypericum polyanthemum

The influences of culture period on growth, plant survival rate and content of phenolic compounds were investigated in vitro and in acclimatized field-grown plants of Hypericum polyanthemum. The growth kinetics of micropropagated plantlets cultured in MS modified medium and the concomitant transference to ex vitro conditions showed that cultures achieved maximum biomass and yield of bioactive compounds after 12 weeks of in vitro growth, with field-grown plants displaying the same survival pattern. Differences in yield among plants cultured in vitro for 8 and 12 weeks that were acclimatized and followed over two years showed that the physiological age of the in vitro cultures influenced biomass production. However, benzopyrans and total phenolic compounds (TPC) contents did not vary significantly, with the exception of the 5-hydroxy-6-isobutyryl-7-methoxy-2,2-dimethyl-benzopyran (HP3) concentration in the reproductive parts, which was higher in the plants grown in vitro for 12 weeks over the two years of the study. All analyzed plant parts from the spring harvest accumulated lower benzopyran levels than plants harvested after 18 weeks of growth in both treatments, except for the levels of 6-isobutyryl-5,7-dimethoxy-2,2-dimethyl-benzopyran (HP1) and 7-hydroxy-6-isobutyryl-5-methoxy-2,2-dimethyl-benzopyran (HP2) in the new vegetative parts of the plants, which did not vary. The concentration of TPC, which was detected at low levels in the old vegetative parts in both treatments, was not altered in other plant parts. The information provided by this work will help structure plant growth and collection periods designed to optimize the yield of each required bioactive metabolite.     

Modulation of the 6-position of benzopyran derivatives and inhibitory effects on the insulin releasing process

The synthesis of different series of 4- and 6-substituted R/S-3,4-dihydro-2,2-dimethyl-2H-1-benzopyrans is described. All of these new benzopyran derivatives were bearing, at the 4-position, a phenylthiourea moiety substituted on the phenyl ring by a meta or a para-electron-withdrawing group such as Cl or CN. The study aimed at exploring the influence of the nature of the substituent at the 6-position in order to develop new benzopyran-type K(ATP) channel activators exhibiting an improved selectivity towards the insulin secreting cells. The original compounds were examined in vitro on rat pancreatic islets (inhibition of insulin release) as well as on rat aorta rings (vasorelaxant effect) and their activity was compared to that of the reference K(ATP) channel activators (±)-cromakalim, (±)-pinacidil, diazoxide and to previously synthesized cromakalim analogues. Structure-activity relationships indicated that the inhibitory effect on the insulin secreting cells was related to the lipophilicity of the molecules and to the size of the substituent located at the 6-position. A marked inhibitory activity on the insulin secretory process was obtained with molecules bearing a bulky tert-butyloxycarbonylamino group at the 6-position (20-23). The latter compounds were found to have the same efficacy on the pancreatic endocrine tissue than some previously described molecules. Lastly, radioisotopic experiments further identified R/S-N-4-chlorophenyl-N'-(6-tert-butyloxycarbonylamino-3,4-dihydro-2,2-dimethyl-2H-1-benzopyran-4-yl)thiourea (23) as a K(ATP) channel opener.     

Two naphthopyran derivatives from Faramea cyanea

Four anthraquinones and two new products, faramol (3,4-dihydro-3-hydroxy-2,2-dimethyl-2H-naphtho[1,2-b]pyran) and 7-methoxyfaramol (3,4-dihydro-3-hydroxy-7-methoxy-2,2-dimethyl-2H-naphtho[l,2-b]pyran), have been isolated from Faramea cyanea.     

Preparation and properties of novel gramicidin S analogs possessing a tri-, tetra- or pentamethylene bridge between ornithine side chains.

Gramicidin S (GS) analogs in which the Ndelta atoms of the two Orn side chains are linked by an oligomethylene bridge [-(CH2)n-; n=3-5] were prepared via the bis(p-nitrobenzenesulfonyl) derivative [Orn(NBS)2,2']GS. For comparison the nonbridged secondary amino group-containing analog [Orn(Me)2,2']GS was also prepared. 1H NMR and CD spectral analysis indicated that these analogs adopt the same beta-sheet conformation as GS. The antimicrobial activities of these analogs were very similar, but were slightly dependent on the bridge chain length, the trimethylene-bridged analog being the most potent.     

New R/S-3,4-dihydro-2,2-dimethyl-2H-1-benzopyrans as KATP channel openers: Modulation of the 4-position

The present work aimed at exploring a series of diversely 4-arylthiourea-substituted R/S-3,4-dihydro-2,2-dimethyl-6-halo-2H-1-benzopyrans structurally related to (±)-cromakalim. These new compounds were examined in vitro as putative potassium channel openers (PCOs) on rat pancreatic islets (inhibition of insulin release) as well as on rat aorta rings (relaxation of aorta ring) and their activity was compared to that of the reference K_ATP channel activators (±)-cromakalim, (±)-pinacidil, diazoxide and of previously reported cromakalim analogues. Structure–activity relationships indicated that the most pronounced inhibitory activity on the insulin secretory process was obtained with molecules bearing a strong meta- or para-electron-withdrawing group (CN or NO₂) on the phenyl ring of the arylthiourea moiety at the 4-position of the benzopyran nucleus (compounds 12–23). Among those, R/S-6-chloro-4-(4-cyanophenylaminothiocarbonylamino)-3,4-dihydro-2,2-dimethyl-2H-1-benzopyran (16) was found to be the most potent benzopyran-type inhibitor of insulin release ever described. Most of these original benzopyran derivatives show increased selectivity for pancreatic versus vascular tissue. Radioisotopic investigations indicated that these new compounds activated pancreatic K_ATP channels.