珙桐科植物化学成分研究进展(综述)

本文概述从珙桐科植物中得到的数十种化合物的结构和波谱数据及药理活性,这些化合物大多结构新颖、具有较强生理活性,主要为喹啉类生物碱、吲哚类生物碱、鞣花酸类化合物、黄酮类化合物以及其它化合物。     

Pregnane alkaloids from Sarcococca ruscifolia and their cytotoxic activity

Six pregnane alkaloids were isolated from the root of Sarcococca ruscifolia. The structures of three new alkaloids, namely, sarcorucinine E–G (1–3), were elucidated using spectroscopic methods, while three known alkaloids, namely, epipachysamine D, pachysamine M, and sarcovagine D, were identified by comparing their spectral data with those of the compounds reported earlier. All compounds were evaluated for their inhibitory activities against multiple types of cancer cells.     

Further Daphniphyllum Alkaloids with Insecticidal Activity from the Bark of Daphniphyllum macropodum Miq.

Two new Daphniphyllum alkaloids, macropodumines J and K ( 1 and 2 , resp.), together with six known structurally related alkaloids, 3 – 8 , were isolated from the bark of Daphniphyllum macropodum Miq . The structures of the new compounds 1 and 2 were elucidated on the basis of a comprehensive analysis of their spectroscopic and chemical data. Macropodumine J ( 1 ) contains a CN group which is relatively rare in naturally occurring alkaloids. All isolated compounds were tested for their insecticidal activities against a number of insect species. Daphtenidine C ( 5 ) is the most active compound against Plutella xylostella. This is the first report of insecticidal properties of Daphniphyllum alkaloids.     

Norditerpenoid alkaloids from the roots of Aconitum heterophyllum Wall with antibacterial activity

Two new aconitine-type norditerpenoid alkaloids 6-dehydroacetylsepaconitine (1) and 13-hydroxylappaconitine (2), along with three known norditerpenoid alkaloids lycoctonine, delphatine and lappaconitine were isolated from the roots of the Aconitum heterophyllum Wall. These compounds exhibited significant antibacterial activity. The structure of compound 1 and 2 were deduced on the basis of their spectral data.     

Norditerpenoid Alkaloids from Aconitum spicatum Stapf

To search for pharmacologically and structurally interesting substances from traditional Chinese medicines, we Investigated the chemical compounds of Aconitum spicatum Stapf. Two new nordlterpenold alkaloids, namely spicatlne A （compound 1） and splcatine B （compound 2）, as well as 11 known norditerpenoid alkaloids were Isolated from the CHCIs portion of the 90% ethanol extract of the roots of A. spicatum. The structures of the alkaloids were characterized on the basis of their spectral data. One of the Isolated compounds showed significant cytotoxic activities （IC50 values 〈 200μmol/l.） against the HL-60 cell line.     

天然C19—二萜生物碱的核磁共振谱（Ⅱ）

本文将迄今为止已发表的230余个天然C_(19)二萜生物碱,按其结构和核磁共振波谱特征分为8个类型,着重叙述了每个类型的结构和核磁共振波谱,并对某些立体构型与~(13)C-NMR化学位移的关系进行了讨论。最后以表格的形式报导了每个天然C_(19)-二萜生物碱的结构及其主要植物来源,并将其中170余个生物碱的~(13)C-NMR化学位移数据分门别类,整理成表,有助于C_(19)-二萜生物碱的结构鉴定。这是本文的第二部分,包括二氧亚甲基型,氨缩醛型,C-18甲基型。C_(18)型不饱和型和内脂型等六个类型的结构特征及其核磁共振波谱。     

Norditerpenoid alkaloids from the roots of Aconitum heterophyllum Wall with antibacterial activity

Two new aconitine-type norditerpenoid alkaloids 6-dehydroacetylsepaconitine (1) and 13-hydroxylappaconitine (2), along with three known norditerpenoid alkaloids lycoctonine, delphatine and lappaconitine were isolated from the roots of the Aconitum heterophyllum Wall. These compounds exhibited significant antibacterial activity. The structure of compound 1 and 2 were deduced on the basis of their spectral data.     

茶叶中生物碱及多酚类化合物高效液相色谱-主成分聚类分析

色谱分析,以结果中该9种组分的相对含量关系为指标建立样本矩阵。应用主成分分析法进行聚类分析。结果很好的反映了不同品种和产地的茶叶的品质差异。     

Bioactive benzylisoquinoline alkaloids from Artabotrys hexapetalus

Two new benzylisoquinoline alkaloids, namely, hexapetalines A (1) and B (2), along with 11 known alkaloids were isolated from the stems of Artabotrys hexapetalus. The structures of 1 and 2 with their absolute configurations were elucidated by extensive spectroscopic methods and the known compounds were identified by comparisons with data in the literature. All new compounds were evaluated for their cytotoxicities against five human cancer cell lines: HL-60, SMMC-7721, A-549, MCF-7 and SW480 in vitro. Alkaloids 1 and 2 exhibited inhibitory effects with IC₅₀ values comparable to those of cisplatin.     

Cytotoxic benzophenanthridine and benzylisoquinoline alkaloids from Argemone mexicana

Fractionation of the chloroform extract from the aerial part of Argemone mexicana led to the isolation of two benzophenanthridine-type alkaloids, N-demethyloxysanguinarine and pancorine; three benzylisoquinoline-type alkaloids, (+)-1,2,3,4-tetrahydro-1-(2-hydroxymethyl-3,4-dimethoxyphenylmethyl)-6,7-methylenedioxyisoquinoline, (+)-higenamine and (+)-reticuline. Among them, N-demethyloxysanguinarine is a new compound, and (+)-1,2,3,4-tetrahydro-1-(2-hydroxymethyl-3,4-dimethoxyphenylmethyl)-6,7-methylenedioxy-isoquinoline was isolated form a natural source for the first time, to which was assigned a trivial name, (+)-argenaxine. In addition, six known non-alkaloidal compounds were also isolated and identified. All compounds were characterized on the basis of their spectral data and chemical evidences. Some isolated alkaloids from this species were evaluated for their cytotoxicity to human nasopharyngeal carcinoma (HONE-1) and human gastric cancer (NUGC) cell lines. Chelerythrine was found to exhibit significant activity against NUGC cell line, while angoline inhibited both types. (+)-Argenaxine showed moderate activity against the NUGC cell line.     

Prenylated indole alkaloids from the stem bark of Hexalobus monopetalus

Seven new prenylated indole alkaloids (1–7) together with two known compounds (8–9) were isolated from the stem bark of Hexalobus monopetalus. Their structures were established on the basis of comprehensive spectroscopic analysis, including HR-MS, 1D and 2D NMR and by comparison of their spectral data with those reported in literature. The new compounds were tested for antimicrobial activity against selected pathogenic bacteria and fungi but showed no activity. The marked presence of prenylated indole alkaloids in Hexalobus and closely related genera makes them useful chemotaxonomic markers.     

Metabolism studies of the Kratom alkaloids mitraciliatine and isopaynantheine, diastereomers of the main alkaloids mitragynine and paynantheine, in rat and human urine using liquid chromatography-linear ion trap-mass spectrometry

Mitragyna speciosa (Kratom in Thai), native in Southeast Asia, is increasingly misused as a herbal drug of abuse. During metabolism studies on the Kratom alkaloids mitragynine, its diastereomers speciogynine and speciociliatine as well as paynantheine in rats and humans, further isomeric compounds were detected in Kratom users' urine. The question arose whether these compounds were formed from the low abundant, isomeric alkaloids mitraciliatine (MC) and isopaynantheine (ISO-PAY). Therefore, the aim of the presented study was to identify using liquid chromatography-linear ion trap-mass spectrometry their phase I and II metabolites in rat urine after administration of pure MC or ISO-PAY, to confirm their formation in humans, and finally to confirm whether the above-mentioned isomeric compounds in human urine represent MC and ISO-PAY and/or their metabolites. The metabolic pathways of both alkaloids in rats were found to be comparable to those of their corresponding diastereomers. In the human urines tested, not all metabolites found in rats could be detected because of the much lower amounts of MC and ISO-PAY in Kratom. However, all the above-mentioned so far unknown isomeric compounds could be identified in the human urine samples as MC, ISO-PAY and/or their metabolites. The used LC separation was also suitable for the differentiation of all other Kratom alkaloids and their metabolites in human urine.     

The alkaloids and other constituents from the root and stem of Aristolochia elegans

Two new aristolactams, aristolactam E (1) and aristolactam-AIIIa-6-O-beta-D-glucoside (2), three novel benzoyl benzyltetrahydroisoquinoline ether N-oxide alkaloids, aristoquinoline A (3), aristoquinoline B (4), and aristoquinoline C (5), and a new biphenyl ether, aristogin F (6), together with 62 known compounds have been isolated from the root and stem of Aristolochia elegans Mast. The structures of the new natural products were established on the basis of spectral evidence. Some of the isolated compounds were examined for their antioxidative and antityrosinase activities. Occurrence of the isoquinolones, biphenyl ethers, and benzoyl benzyltetrahydroisoquinoline ether alkaloids in the same plant indicated the definite possibility of these metabolites as biotransformation intermediates of bisbenzyltetrahydroisoquinoline alkaloids. This can be useful to solve the catabolic process of bisbenzyltetrahydroisoquinoline alkaloids.     

New cholinesterase-inhibiting triterpenoid alkaloids from Buxus hyrcana

The current phytochemical investigation on Buxus hyrcana Pojark. has resulted in the isolation of the triterpenoid alkaloids 1-10. The structures of five new alkaloids, hyrcanone (1), hyrcanol (2), hyrcatrienine (3), N(b)-dimethylcycloxobuxoviricine (4), and hyrcamine (5), were elucidated by means of modern spectroscopic techniques, while the known alkaloids, buxidin (6), buxandrine (7), buxabenzacinine (8), buxippine-K (9) and E-buxenone (10), were identified by comparing their spectral data with those reported earlier. Compounds 1 and 3-9 were found to be acetyl- and butyrylcholinesterase inhibitors. The IC50 values were estimated to be in the range of 83.0-468.0 microM against AChE and 1.12-350.0 microM against BChE. The structure-activity relationship studies suggested that the presence of dimethylamino moieties at C(3) and C(20) is the most important factor influencing the activity of these compounds against the cholinesterase enzymes. All compounds were also evaluated for cytotoxicity on a fibroblast cell line with incubation of 24 h. No cytotoxic effects were exerted by any compound.     

Rare Bisindole Alkaloids from the Amazonian Tree Raputia simulans

The stem bark of Raputia simulans (Rutaceae) has been reported to contain simple and dimeric indole alkaloids. Further phytochemical investigation of R. simulans stem bark resulted in the isolation of three new alkaloids. These compounds represent a relatively new category of dimeric indole alkaloids with a cyclohexene moiety in their core. Their structure elucidations were based on NMR and HR‐MS techniques, while structural aspects concerning their relative configuration were investigated using molecular mechanics calculations and NOESY experiments.     

The effect of alkaloids on sugar receptors and the feeding behaviour of the blowfly

ABSTRACT. The deterrent effect of alkaloids on feeding by the black blowfly Phormia regina Meigen (Diptera: Calliphoridae) was tested by determining tarsal thresholds for mixtures of sucrose and alkaloids. The following alkaloids were used: atropine sulphate, berberine sulphate, quinine mono-hydrochloride, caffeine, yohimbine sulphonic ester, pilocarpine hydrochloride, coniine hydrochloride and codeine. The same alkaloids were tested electrophysiologically on tarsal chemoreceptors (D hairs). Both behaviourally and electrophysiologically alkaloids reduced response to sucrose. Deterrence and peripheral inhibition could be blocked by increasing the concentration of sucrose. Application of kinetic analyses to the electrophysiological data ruled out competitive, non-competitive, and uncompetitive inhibition at receptor sites. There is no correlation of thresholds with available data on lipid solubility or octanol/water partition coefficients. The diverse pharmacological properties of alkaloids suggest that there is no uniform limiting mechanism for this multiform array of compounds.     

Phytochemical and chemotaxonomic study on Dictamnus angustifolius G. Don ex Sweet (Rutaceae)

A phytochemical investigation of Dictamnus angustifolius led to the isolation of 14 compounds, including six furoquinoline alkaloids (1–6), two sesquiterpenoids (7, 8) and six flavonoids (9–14). The structures of these compounds were identified by spectroscopic methods and a comparison of their data with those reported in the literature. This is the first report of three furoquinoline alkaloids 1–3 and six flavonoids 9–14 from the genus Dictamnus and the first isolation of compounds 4–8 from D. angustifolius. The chemotaxonomic significance of furoquinoline alkaloids and sesquiterpenoids has also been summarized.     

Novel bioactive bromopyrrole alkaloids from the Mediterranean sponge Axinella verrucosa

The Mediterranean sponge Axinella verrucosa has been investigated for its alkaloid composition and has been found to produce a complex mixture of bromopyrrole alkaloids. Along with the previously isolated compounds 5-18, four novel alkaloids of this class, compounds 1-4, have been isolated, and their structures established through spectroscopic methods. Compounds 1-4 were found to display neuroprotective activity against the agonists serotonin and glutamate in vitro.     

Medicinal plants: Concentrators and superconcentrators of copper and its role in metabolism of these species

With the combination of the atomic absorption method and spectrophotometry, we conducted the testing of medicinal plants of Russian flora (approximately 200 species) on the content of copper (Cu). We revealed 36 species—concentrators and superconcentrators of this element. The capability of these species to accumulate Cu is compared with the synthesis of physiologically active compounds (PAC), among which alkaloids and phenolic compounds prevail. The stimulating influence of Cu on the formation and accumulation of alkaloids of main structural types—derivatives of chinolysidine, isochinoline, tropane, and indole—is established. The data about the role of Cu-containing enzymes in the metabolism of alkaloids, as well as of phenolic compounds, are reviewed on the example of flavonoids. The role of concentrated copper in the medicinal effect of medicinal plants and, thus, the appearing perspective to widen their application spectrum, especially in the cases when the orientation of the action of PAC and Cu are different, is discussed.     

Structural analogs of tylophora alkaloids may not be functional analogs

Phenanthroindolizidine-based tylophora alkaloids have been reported to have potential antitumor, anti-immuno and, anti-inflammatory activity. The structure-activity relationships of a series of tylophora alkaloids were studied to guide future drug design. Our results indicate that although these compounds are structural analogs, their potency of cytotoxicity, selectivity against NF-kappaB signaling pathway, and their inhibitory effects against protein and nucleic acid synthesis are different. Because they do not have an identical spectrum of targets, the studied compounds are structural, but may not be functional analogs.