长梗千里光中的呋喃雅槛兰型倍半萜

长梗千里光（ＳｅｎｅｃｉｏｋａｓｃｈｋａｒｏｖｉｉＣ．Ｗｉｎｋｌ．）为菊科千里光属的多年生草本植物,广布于甘肃省东南部的灌木丛中及林边草地,四川、青海也有分布［１］。其化学成分未见报道。千里光属植物的主要成分是双稠吡咯啶生物碱和呋喃雅槛兰型倍半萜［２,３］。前者具有抗癌活性,但也有致癌、致畸等毒性［４］。我们从长梗千里光的地上部分分离到两个呋喃雅槛兰型倍半萜（１）和（２）,通过ＵＶ、ＩＲ、ＭＳ、１Ｈ－ＮＭＲ和１３Ｃ－ＮＭＲ等光谱分析,确定化合物１为１α－乙酰氧基－６β－当归酰氧基－１０β－羟基－…     

新疆千里光的化学成分研究北大核心CSCD

本文对新疆千里光进行了化学成分研究,从中分离鉴定了12个化合物,分别为千里光碱（1）、千里光菲灵碱（2）、全缘千里光碱（3）、克式千里光碱（4）、异鼠李素（5）、槲皮素（6）、异鼠李素-3—O-β-D-半乳糖苷（7）、8-（2＂-pyrrolidinone-5”-y1）-isorhamnetin（8）、pseudotaraxasterc1（9）、咖啡酸（10）、β-谷甾醇（11）、卢-胡萝卜苷（12）。除1—3外,其余9个化合物均为首次从该植物中分离得到。     

麻叶千里光抗菌化学成分的研究(Ⅲ)

以革兰氏阳性菌金黄色葡萄球菌（Staphylococcus aureus）、枯草芽孢杆菌（Bacillus subtilis）和阴性菌大肠杆菌（Escherichia coli）为受试菌,采用体外抑菌圈法追踪抗菌活性部分。利用各种色谱技术对正丁醇萃取部分进行分离纯化,根据理化性质和谱学数据进行结构鉴定。从麻叶千里光的水提醇沉物的正丁醇萃取部分分离得到3个化合物：苄基-O-α-L-广吡喃阿拉伯糖基（1→6）-β-D-吡喃葡糖苷（1）、（6S,9S）-6-羟基-3-酮-α-紫罗兰醇-9-O-β-D-葡糖苷（2）和（6S,9R）-6-羟基-3-酮-α-紫罗兰醇-9-O-β-D-葡糖苷（3）。它们均为首次从该属植物中分离得到。     

白粉藤的木脂素和三萜成分

从白粉藤（Cissus repens Lank）地上部分分离得到5个木脂素和8个三萜,其中一个木脂素是新化合物,它的结构通过波谱分析和碱水解的方法鉴定为：（＋）-异落叶松树脂醇-9′-（2-对-香豆酰）-O-β-D-吡喃木糖苷（1）。其余化合物分别是：（＋）-异落叶松树脂醇-9′-O-β-D-吡喃木糖苷（2）,（＋）-Lyoniside（3）,（—）-开环异落叶松树脂醇-9-O-β-D-吡喃木糖苷（4）,（7′R,8′S）-4′-hydroxy-3′,5-dimethoxy-7,8′-dihydrobenzofuran-1-propanolneolignan-9′-O-β-D-xylopyranoside（5）,木栓酮（6）,表木栓醇（7）,蒲公英赛醇乙酸酯（8）,熊果酸（9）,2α-羟基乌索酸（10）,积雪草酸（11）,Niga-ichigoside F1（12）,羽扇豆醇（13）。这些化合物都是首次从该植物中分离得到。     

紫花苜蓿化学成分的研究(英文)

为研究紫花苜蓿（Medicago scttiva L．）地上部位的化学成分,通过溶剂萃取、硅胶柱色谱、凝胶柱色谱分离纯化,从紫花苜蓿地上部分分离得到9个化合物,根据质谱和核磁共振数据鉴定为小檗碱（1）、大黄素（2）、大黄素8-O-β-D-葡萄糖苷（3）、soyαsαpogenol B-3-O-β-glcA（4）、邻羟基苯甲酸（5）、反式对羟基肉挂酸（6）、顺式对羟基肉桂酸（7）、正三十烷醇（8）和β-胡萝卜苷（9）。其中化合物1—4为首次从苜蓿属植物中分离得到。     

掌裂橐吾的胚胎学

首次报道了掌裂橐吾的胚胎发育过程。药壁发育双子叶型;绒毡层发育属、The Cosmos bipinnatus”型,成熟花粉为3细胞型;单珠被,薄珠心,倒生胚珠;具发达的珠被绒毡层;胚囊发育为4孢子型,类似德鲁撒型（Drusa);胚乳发育为核型,胚胎发育为紫菀型千里光变型。     

吡咯喹啉醌的生物合成及其应用

70年代以前,发现有的细菌甲醇脱氨酶（MDH）辅基的某些性质与喋啶的相似,猜测其是一种喋啶衍生物。直到1979年,Salishury等［1］采用X-射线衍射技术,分析了假单胞菌（Pseudomonassp．）TPIMDH辅基的丙酮加成物晶体结构,才首次阐明该辅基的分子结构,并命名为吡咯喹啉醌（P     

海南染木树茎的化学成分研究(Ⅰ)北大核心CSCD

研究海南染木树茎的化学成分,采用硅胶、Sehadex LH-20、ODS、HPLC等色谱技术对海南染木树茎乙醇提取物的乙酸乙酯部位进行分离和纯化,结合光谱数据和理化性质鉴定化合物的结构,分别为：4-甲基苯并喹啉-5,10-二酮（1）、白兰花碱（2）、鹅掌楸碱（3）、吲哚-3-甲醛（4）、羽扇豆醇（5）、霍烷-3,30-二醇（6）、熊果酸（7）、白桦酯酸（8）、30-羟基羽扇豆醇（9）、豆甾醇（10）、3β-乙酰基齐墩果醛（11）。其中,化合物4、7为首次从染木树属植物中分离得到,5、6、8、9-11为首次从该植物中分离得到。首次对化合物2的碳谱数据进行了归属。     

牛尾草中一新的对映-贝壳杉烷型二萜

从牛尾草[Isodon ternifolius(D.Don)Kudo]的地上部分分离得到一个新的对映－贝壳杉烷型二萜,命名为牛尾草素H（1）,通过波谱方法鉴定了它的结构。此外,还分离得到5个已知的对映－贝壳杉烷型二萜化合物：香茶菜醛（2）,长管香茶菜素A,E和G（3－5）,开展香茶菜素E（6）,以及木樨草素（7）,芹菜素（8）,α－香树脂醇（9）,乌索酸（10）和2α－羟基乌索酸（11）。     

植物中吡咯里西啶生物碱的检测与分析

吡咯里西啶生物碱广泛分布于植物界。很多吡咯里西啶生物碱对动物和人类有严重的毒性作用,包括肝脏毒性,肺脏毒性,致癌作用,致突变作用和神经毒性等。本文综述了植物中吡咯里西啶生物碱的分离,纯化,检测与分析。     

Occurrence of pyrrolizidine alkaloids in three Ethiopian Solanecio species

Three Ethiopian Solanecio species, namely Solanecio angulatus (Vahl) C. Jeffrey, Solanecio mannii (Hook. f.) C. Jeffrey, and Solanecio tuberosus (Sch. Bip. ex A. Rich.) C. Jeffrey var. tuberosus were analysed by capillary gas chromatography–mass spectrometry (GLS–MS) for their pyrrolizidine alkaloid content. All the extracts investigated contain pyrrolizidine alkaloids. Whilst only traces of alkaloids could be detected in the leaf extract of S. angulatus, the content of alkaloids in the other samples ranged between 0.13% dry weight (for the flowers of S. angulatus) and 0.58% (for the tubers of S. tuberosus). Altogether 17 alkaloids were detected out of which 14 were unambiguously identified by comparing their retention indices, molecular masses and mass fragmentation patterns with defined reference data from PAs database or in some cases with reference compounds. The hepatotoxic macrocyclic diesters senecionine and retrosine figured as major alkaloids in the flowers of S. angulatus, whereas the platynecine type alkaloid, 7-O-senecioylplatynecine occurred in higher amount than the other alkaloids detected in the leaves of S. mannii. The tuberous annual herb, S. tuberosus contains eruciflorine as a major alkaloid in the leaves, flowers and tubers. Senecionine figures as one of the major components of the tubers of S. tuberosus. To the best of our knowledge this is the first published report on the occurrence of pyrrolizidine alkaloids in the genus Solanecio. In addition to the chemotaxonomic significance of the detected alkaloids, a brief remark is made on the findings in the light of the use of these plants as medicinal herbs and/or as nectar or pollen source for the production of honey.     

Biochemical strategy of sequestration of pyrrolizidine alkaloids by adults and larvae of chrysomelid leaf beetles

Tracer feeding experiments with (14)C-labeled senecionine and senecionine N-oxide were carried out to identify the biochemical mechanisms of pyrrolizidine alkaloid sequestration in the alkaloid-adapted leaf beetle Oreina cacaliae (Chrysomelidae). The taxonomically closely related mint beetle (Chrysolina coerulans) which in its life history never faces pyrrolizidine alkaloids was chosen as a 'biochemically naive' control. In C. coerulans ingestion of the two tracers resulted in a transient occurrence of low levels of radioactivity in the hemolymph (1-5% of radioactivity fed). With both tracers, up to 90% of the radioactivity recovered from the hemolymph was senecionine. This indicates reduction of the alkaloid N-oxide in the gut. Adults and larvae of O. cacaliae sequester ingested senecionine N-oxide almost unchanged in their bodies (up to 95% of sequestered total radioactivity), whereas the tertiary alkaloid is converted into a polar metabolite (up to 90% of total sequestered radioactivity). This polar metabolite, which accumulates in the hemolymph and body, was identified by LC/MS analysis as an alkaloid glycoside, most likely senecionine O-glucoside. The following mechanism of alkaloid sequestration in O. cacaliae is suggested to have developed during the evolutionary adaptation of O. cacaliae to its alkaloid containing host plant: (i) suppression of the gut specific reduction of the alkaloid N-oxides, (ii) efficient uptake of the alkaloid N-oxides, and (iii) detoxification of the tertiary alkaloids by O-glucosylation. The biochemical mechanisms of sequestration of pyrrolizidine alkaloid N-oxides in Chysomelidae leaf beetles and Lepidoptera are compared with respect to toxicity, safe storage and defensive role of the alkaloids.     

Independent recruitment of a flavin-dependent monooxygenase for safe accumulation of sequestered pyrrolizidine alkaloids in grasshoppers and moths

Several insect lineages have developed diverse strategies to sequester toxic pyrrolizidine alkaloids from food-plants for their own defense. Here, we show that in two highly divergent insect taxa, the hemimetabolous grasshoppers and the holometabolous butterflies, an almost identical strategy evolved independently for safe accumulation of pyrrolizidine alkaloids. This strategy involves a pyrrolizidine alkaloid N-oxygenase that transfers the pyrrolizidine alkaloids to their respective N-oxide, enabling the insects to avoid high concentrations of toxic pyrrolizidine alkaloids in the hemolymph. We have identified a pyrrolizidine alkaloid N-oxygenase, which is a flavin-dependent monooxygenase, of the grasshopper Zonocerus variegatus. After heterologous expression in E. coli, this enzyme shows high specificity for pyrrolizidine alkaloids of various structural types and for the tropane alkaloid atropine as substrates, a property that has been described previously for a pyrrolizidine alkaloid N-oxygenase of the arctiid moth Grammia geneura. Phylogenetic analyses of insect flavin-dependent monooxygenase sequences suggest that independent gene duplication events preceded the establishment of this specific enzyme in the lineages of the grasshoppers and of arctiid moths. Two further flavin-dependent monooxygenase sequences have been identified from Z. variegatus sharing amino acid identities of approximately 78% to the pyrrolizidine alkaloid N-oxygenase. After heterologous expression, both enzymes are also able to catalyze the N-oxygenation of pyrrolizidine alkaloids, albeit with a 400-fold lower specific activity. With respect to the high sequence identity between the three Z. variegatus sequences this ability to N-oxygenize pyrrolizidine alkaloids is interpreted as a relict of a former bifunctional ancestor gene of which one of the gene copies optimized this activity for the specific adaptation to pyrrolizidine alkaloid containing food plants.     

Testing chemical defence based on pyrrolizidine alkaloids

Pyrrolizidine alkaloids are considered the primary defence mechanism in aposematic ithomiine butterflies and arctiid moths. Despite evidence that pyrrolizidine alkaloids are effective against some invertebrate predators, proof for a protective function of pyrrolizidine alkaloids against vertebrate predators is fragmented. The present work shows that the pyrrolizidine alkaloid monocrot-aline is unpalatable to the pileated finch,Coryphospingus pileatusand that the unpalatability is learned through association with a specific colour pattern (blue stripes). In a series of trials, using mealworms as model prey, birds rejected those to which pyrrolizidine alkaloid solution had been applied topically but accepted prey devoid of the alkaloid. Subsequent offerings of prey with pyrrolizidine alkaloid and a painted blue-striped pattern led to consistent rejections by the experimental birds. Birds were then offered blue-striped painted larvae without pyrrolizidine alkaloids (‘mimics’), which were rejected at levels similar to the previous trial. The predators learned to recognize the prey as unpalatable items based on their experience in the previous encounters. These results provide evidence for the protective capacity of the pyrrolizidine alkaloid against a vertebrate predator and supports the role of these chemicals in aposematism in the Lepidoptera.     

Tissue distribution and biosynthesis of 1,2-saturated pyrrolizidine alkaloids in Phalaenopsis hybrids (Orchidaceae)

Phalaenopsis hybrids contain two 1,2-saturated pyrrolizidine monoesters, T-phalaenopsine (necine base trachelanthamidine) and its stereoisomer Is-phalaenopsine (necine base isoretronecanol). T-Phalaenopsine is the major alkaloid accounting for more than 90% of total alkaloid. About equal amounts of alkaloid were genuinely present as free base and its N-oxide. The structures were confirmed by GC-MS. The quantitative distribution of phalaenopsine in various organs and tissues of vegetative rosette plants and flowering plants revealed alkaloid in all tissues. The highest concentrations were found in young and developing tissues (e.g., root tips and young leaves), peripheral tissues (e.g., of flower stalks) and reproductive organs (flower buds and flowers). Within flowers, parts that usually attract insect visitors (e.g., labellum with colorful crests as well as column and pollinia) show the highest alkaloid levels. Tracer feeding experiments with (14)C-labeled putrecine revealed that in rosette plants the aerial roots were the sites of phalaenopsine biosynthesis. However active biosynthesis was only observed in roots still attached to the plant but not in excised roots. There is a slow but substantial translocation of newly synthesized alkaloid from the roots to other plant organs. A long-term tracer experiment revealed that phalaenopsine shows neither turnover nor degradation. The results are discussed in the context of a polyphyletic molecular origin of the biosynthetic pathways of pyrrolizidine alkaloids in various scattered angiosperm taxa. The ecological role of the so called non-toxic 1,2-saturated pyrrolizidine alkaloids is discussed in comparison to the pro-toxic 1,2-unsaturated pyrrolizidine alkaloids. Evidence from the plant-insect interphase is presented indicating a substantial role of the 1,2-saturated alkaloids in plant and insect defense.     

Experience influences gustatory responsiveness to pyrrolizidine alkaloids in the polyphagous caterpillar,Estigmene acrea

Electrophysiological recordings from taste sensilla of the caterpillar Estigmene acrea with the pyrrolizidine alkaloid, seneciphylline N-oxide, demonstrated that prior feeding on plants with pyrrolizidine alkaloids caused an increase in responsiveness of the PA-sensitive cells in two sensilla, relative to feeding on plants without such chemicals. Rearing on synthetic diet without pyrrolizidine alkaloids for up to seven generations caused a continuous decline in responsiveness, that could be reversed by experience with powdered Crotalaria pumila in the diet or by pure pyrrolizidine alkaloid, monocrotaline, in the diet. Response to the cardiac glycoside, ouabain, that stimulates one of the two pyrrolizidine alkaloid-sensitive cells, showed a similar decline. Pyrrolizidine alkaloids had no measurable effect on growth and development. Responses in all other taste cells were unaffected. The data are discussed in relation to the possible adaptive significance and the possible mechanisms involved.R.F. Chapman has died since this article was written     

The evolution of pyrrolizidine alkaloid diversity among and within Jacobaea species

Plants produce many secondary metabolites showing considerable inter- and intraspecific diversity of concentration and composition as a strategy to cope with environmental stresses. The evolution of plant defenses against herbivores and pathogens can be unraveled by understanding the mechanisms underlying chemical diversity. Pyrrolizidine alkaloids are a class of secondary metabolites with high diversity. We performed a qualitative and quantitative analysis of 80 pyrrolizidine alkaloids with liquid chromatography-tandem mass spectrometry of leaves from 17 Jacobaea species including one to three populations per species with 4–10 individuals per population grown under controlled conditions in a climate chamber. We observed large inter- and intraspecific variation in pyrrolizidine alkaloid concentration and composition, which were both species-specific. Furthermore, we sequenced 11 plastid and three nuclear regions to reconstruct the phylogeny of the 17 Jacobaea species. Ancestral state reconstruction at the species level showed mainly random distributions of individual pyrrolizidine alkaloids. We found little evidence for phylogenetic signals, as nine out of 80 pyrrolizidine alkaloids showed a significant phylogenetic signal for Pagel's λ statistics only, whereas no significance was detected for Blomberg's K measure. We speculate that this high pyrrolizidine alkaloid diversity is the result of the upregulation and downregulation of specific pyrrolizidine alkaloids depending on ecological needs rather than gains and losses of particular pyrrolizidine alkaloid biosynthesis genes during evolution.     

Influence of Endophyte and Water Regime Upon Tall Fescue Accessions. II. Pyrrolizidine and Ergopeptine Alkaloids

Alkaloids, along with specific environmental conditions, havebeen associated with both detrimental and beneficial aspectsof endophyte (Acremonium coenophialum Morgan-Jones et Gams)infected tall fescue (Festuca arundinacea Schreb.) associations.Benefits to the plant accrue through reduced herbivory, whereasdetriment to the animal occurs as altered grazing behaviourand reduced productivity. A controlled environment study wasconducted to examine pyrrolizidine and ergopeptine alkaloidconcentration of four tall fescue accessions as influenced byendophyte status and water regime. Endophyte-free plants weredevoid of ergopeptine alkaloid and contained little, if any,pyrrolizidine alkaloid. Leaf blade tissue of endophyte-infectedisolines contained a range of both ergopeptine (256 to 1633ng g^–1) and pyrrolizidine (92 to 450 µg g^–1)alkaloid concentrations. Water deficit generally increased alkaloidconcentration. Alkaloid yield, based upon concentration andtissue d. wt, showed that significant increase in ergopeptineand pyrrolizidine alkaloid in leaf tissue was associated withwater deficit and was due to actual increased synthesis andnot simply decreased phytomass. Leaf and pseudostem (leaf sheathand stem base) tissue alkaloid concentrations indicated differentaccumulation patterns for ergopeptine and pyrrolizidine alkaloids.Ergopeptine alkaloid yield increased in water-stressed pseudostem,whereas pyrrolizidine alkaloid yield decreased in some, butnot all accessions. The range of host genotype/endophyte biotyperesponse offers the possibility to select associations whichproduce few deleterious effects in animals yet maintain highforage productivity and persistence. Festuca arundinacea, Acremonium coenophialum, tall fescue genotypes, water stress, N-formyl and N-acetyl loline, ergovaline     

Selective uptake of pyrrolizidine N-oxides by cell suspension cultures from pyrrolizidine alkaloid producing plants

The N-oxides of pyrrolizidine alkaloids such as senecionine or monocrotaline are rapidly taken up and accumulated by cell suspension cultures obtained from plants known to produce pyrrolizidines, i.e. Senecio vernalis, vulgaris, viscosus (Asteraceae) and Symphytum officinale (Boraginaceae). The transport of the N-oxides into the cells is a specific and selective process. Other alkaloid N-oxides such as sparteine N-oxide are not taken up. Cell cultures from plant species which do not synthesize pyrrolizidine alkaloids are unable to accumulate pyrrolizidine N-oxides. The suitability of the pyrrolizidine N-oxides in alkaloid storage and accumulation is emphasized.     

Pyrrolizidine alkaloid biosynthesis,evolution of a pathway in plant secondary metabolism

The system of pyrrolizidine alkaloids has proven to be a powerful system for studying the evolution of a biosynthetic pathway in plant secondary metabolism. Pyrrolizidine alkaloids are typical plant secondary products produced by the plant as a defense against herbivores. The first specific enzyme, homospermidine synthase, has been shown to have evolved by duplication of the gene encoding deoxyhypusine synthase, which is involved in primary metabolism. Despite the identical function of homospermidine synthase for pyrrolizidine alkaloid biosynthesis in the various plant lineages, this gene duplication has occurred several times independently during angiosperm evolution. After duplication, these gene copies diverged with respect to gene function and regulation. In the diverse plant lineages producing pyrrolizidine alkaloids, homospermidine synthase has been shown to be expressed in a variety of tissues, suggesting that the regulatory elements were recruited individually after the duplication of the structural gene. The molecular, kinetic, and expression data of this system are discussed with respect to current models of gene and pathway evolution.