A chlorinated amide and piperidine alkaloids from Aloe sabaea

Phytochemical investigations of Aloe sabaea afforded a new chlorinated amide, N-4'-chlorobutylbutyramide, and the toxic piperidine alkaloids coniine, gamma-coniceine and the quarternary N,N-dimethylconiine. This is the first report of the occurrence of a chlorinated compound in the Aloeaceae family.     

Plant alkaloids that cause developmental defects through the disruption of cholinergic neurotransmission

The exposure of a developing embryo or fetus to alkaloids from plants, plant products, or plant extracts has the potential to cause developmental defects in humans and animals. These defects may have multiple causes, but those induced by piperidine and quinolizidine alkaloids arise from the inhibition of fetal movement and are generally referred to as multiple congenital contracture‐type deformities. These skeletal deformities include arthrogyrposis, kyposis, lordosis, scoliosis, and torticollis, associated secondary defects, and cleft palate. Structure‐function studies have shown that plant alkaloids with a piperidine ring and a minimum of a three‐carbon side‐chain α to the piperidine nitrogen are teratogenic. Further studies determined that an unsaturation in the piperidine ring, as occurs in gamma coniceine, or anabaseine, enhances the toxic and teratogenic activity, whereas the N‐methyl derivatives are less potent. Enantiomers of the piperidine teratogens, coniine, ammodendrine, and anabasine, also exhibit differences in biological activity, as shown in cell culture studies, suggesting variability in the activity due to the optical rotation at the chiral center of these stereoisomers. In this article, we review the molecular mechanism at the nicotinic pharmacophore and biological activities, as it is currently understood, of a group of piperidine and quinolizidine alkaloid teratogens that impart a series of flexure‐type skeletal defects and cleft palate in animals. Birth Defects Research (Part C) 99:235–246, 2013. Published 2013 Wiley Priodicals, Inc.     

Phytochemicals: the good, the bad and the ugly?

Phytochemicals are constitutive metabolites that enable plants to overcome temporary or continuous threats integral to their environment, while also controlling essential functions of growth and reproduction. All of these roles are generally advantageous to the producing organisms but the inherent biological activity of such constituents often causes dramatic adverse consequences in other organisms that may be exposed to them. Nevertheless, such effects may be the essential indicator of desirable properties, such as therapeutic potential, especially when the mechanism of bioactivity can be delineated. Careful observation of cause and effect, followed by a coordinated approach to identify the responsible entities, has proved extremely fruitful in discovering roles for phytochemical constituents. The process is illustrated by selected examples of plants poisonous to animals and include the steroidal alkaloid toxin of Veratrum californicum (Western false hellebore), piperidine alkaloids of Lupinus species (lupines), and polyhydroxy indolizidine, pyrrolizidine and nortropane alkaloids of Astragalus and Oxytropis species (locoweeds), Castanospermum australe (Moreton Bay chestnut) and Ipomoea species (morning glories).     

Separation and measurement of plant alkaloid enantiomers by RP-HPLC analysis of their Fmoc-Alanine analogs

Introduction . Ammodendrine ( 1 ), anabasine ( 2 ) and coniine ( 3 ) can cause congenital malformations in livestock. They appear naturally in both enantiomeric forms, and can cause variable physiological responses. A method to measure the enantiomeric ratio of these natural toxins is needed. Objective . To develop a simple and economical method in order to determine the enantiomeric ratios of piperidine and pyrrolidine alkaloids in small samples of plant material. Methodology . Mixtures of isolated or purified plant alkaloids were converted to their Fmoc‐l ‐Ala‐alkaloid analogues forming diastereomeric mixtures, which were then analysed by high pressure liquid chromatography (HPLC) with mass spectrometry (MS) and ultraviolet (UV) detection to determine enantiomeric ratios. Results . The diastereomeric analogs for ammodendrine, anabasine and nornicotine could be separated and the enantiomeric ratios determined. The Fmoc‐l ‐Ala‐coniine analogue was not resolved under the HPLC conditions studied. The enantiomeric ratios of the selected plant alkaloids were measured and found to differ between both location within a species and location between species. Conclusion . A low‐cost HPLC method to analyse the enantiomeric ratio of plant alkaloids containing primary or secondary amine nitrogens via conversion to their respective diastereomeric analogues has been developed. Published in 2008 by John Wiley & Sons.     

小陇山有毒被子植物调查

据调查统计,甘肃小陇山有毒被子植物共107种,其有毒化学成分主要为非蛋白质氨基酸、肽类、生物碱、酚类衍生物、萜类、甙类和无机及有机物等.对有毒植物的民间用毒、解毒方法进行了调查.     

Host plant selection by a monophagous herbivore is not mediated by quantitative changes in unique plant chemistry: Agonopterix alstroemeriana and Conium maculatum

Host plant selection by ovipositing females is a key process determining the success of phytophagous insects. In oligophagous lepidopterans, host-specific plant secondary chemicals are expected to be dominant factors governing oviposition behavior; distinctive compounds can serve as high-contrast signals that clearly differentiate confamilial hosts from non-hosts increasing the accuracy of host quality evaluation. Agonopterix alstroemeriana (Clerk) (Lepidoptera: Oecophoridae) and Conium maculatum L. (Apiaceae) form an extremely specialized plant-herbivore system, with A. alstroemeriana monophagous on C. maculatum, a plant with few other insect herbivores at least in part due to its virtually unique capacity among plants to produce piperidine alkaloids. Here we have studied the response of A. alstroemeriana oviposition to unique host plant secondary metabolites, piperidine alkaloids, and widespread compounds, mono- and sesquiterpenes, in a concentration-dependent fashion. Rates of oviposition were negatively correlated with Z-ocimene concentrations. To confirm the deterrent properties of this monoterpene for A. alstroemeriana oviposition, we conducted a choice experiment using artificially damaged C. maculatum plants, with higher emission of volatiles, and undamaged control plants. Damaged plants were less preferred as oviposition sites compared to the controls. The lack of association between oviposition and piperidine alkaloids, defenses unique to Conium species, suggests that quantitative changes of these species-specific chemicals do not play a predominant role in host selection by the monophagous A. alstroemeriana.     

Ancistrolikokine D,a 5,8'-coupled naphthylisoquinoline alkaloid,and related natural products from Ancistrocladus likoko

A new naphthylisoquinoline alkaloid, ancistrolikokine D, and the likewise 5,8'-coupled alkaloid ancistroealaine A, as well as two further, biosynthetically related, but nitrogen-free natural products, ancistronaphthoic acid B and cis-isoshinanolone, have been isolated from Ancistrocladus likoko J. LEACUTE;ONARD (Ancistrocladaceae). The 5,8'-coupling of the new alkaloids and of the alkaloids isolated earlier hints at a close phylogenetic relationship of A. likoko to other Central African Ancistrocladus species. The compounds show moderate activities against Leishmania donovani, Trypanosoma cruzi, and Trypanosoma brucei rhodesiense.     

青藏高原东南部天然草地主要有毒植物调查研究

对青藏高原东南部的川西北天然草地主要有毒植物的种类、毒物成分和分布作了系统的调查与研究,首次报道了该区域天然草地有毒植物名录,统计出该区主要有毒植物226种,隶属于33科77属。有毒植物所含主要毒物成分可分为生物碱、苷类化合物、萜类化合物、苯酮类化合物、酚类及其衍生物和简单有机物等6大类。有毒植物在亚高山草甸草地中分布最多,有157种,其次是亚高山灌丛草地、高山草甸草地、高山灌丛草地和高寒沼泽化草甸草地。本调查研究为青藏高原东南部天然草地主要有毒植物的防除和开发利用奠定了基础。     

Alkaloids of Solanaceae (nightshade plants)

Alkaloids are nitrogen containing compounds found in many plants. They are products of plants secondary metabolism derived from amino acids, purines, pyrimidines or terpene. Most of them are drugs. The biological activity of some alkaloids has led to their intensive exploitation by humans, as pharmaceuticals, narcotics or poisons. During the past 30 years, major technical advances have led to substantial progress in our understanding of alkaloid biochemistry, but since then biosynthetic pathways of some alkaloids are not explained. The nightshade (Solanaceae) are widespread family of plants containing tropane alkaloids or glycoalkaloids. Both of them are naturally produced, as a defense mechanism against insects, predator and disease. On the other hand, most of the species of Solanaceae family have been used by human since several centuries.     

Chemical tools to distinguish the fire ant species Solenopsis invicta and S. saevissima (Formicidae: Myrmicinae) in Southeast Brazil

Morphologically similar fire ants Solenopsis invicta and Solenopsis saevissima are broadly sympatric in southeastern Brazil. Chemistry from venom (2,6-dialkyl piperidine alkaloids) and cuticular hydrocarbons have been reported as potentially important tools for differentiating Solenopsis species. We have analysed two chemical classes in widely separated populations of S. invicta and S. saevissima and find that both piperidine alkaloids and cuticular hydrocarbons separate the two species. Piperidine alkaloids clustered S. invicta but not S. saevissima. Cuticular hydrocarbons strongly clustered both S. invicta and S. saevissima. One population morphologically identified as S. invicta presented piperidine alkaloids and cuticular hydrocarbons markedly different from either species. The distinctive piperidine alkaloid differences among populations of S. saevissima and the marked difference in piperidine alkaloid and hydrocarbon profiles of the anomalous population of S. invicta suggest undescribed species fire ant in southeastern Brazil.     

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.     

A new alkaloid from south african Conium species

Recent screening of South African Conium species for alkaloids as part of taxonomic studies has yielded γ-coniceine, coniine, methylconiine, conhydrine and a new alkaloid N-methylpseudoconhydrine. The relative stereochemistry of N-methylpseudoconhydrine was ascertained by ¹H NMR decoupling experiments. This latter alkaloid was found in significant amounts in the leaf and stem of some plants investigated and was the major alkaloid along with conhydrine in the leaf and stem of one group of high altitude plants. These plants also contained significant amounts of volatile oil, the major monoterpene being myrcene.     

Pyrrolizidine alkaloids in human diet.

Pyrrolizidine alkaloids are the leading plant toxins associated with disease in humans and animals. Upon ingestion, metabolic activation in liver converts the parent compounds into highly reactive electrophiles capable of reacting with cellular macromolecules forming adducts which may initiate acute or chronic toxicity. The pyrrolizidine alkaloids present a serious health risk to human populations that may be exposed to them through contamination of foodstuffs or when plants containing them are consumed as medicinal herbs. Some pyrrolizidine alkaloids (PA) adducts are persistent in animal tissue and the metabolites may be re-released and cause damage long after the initial period of ingestion. PAs are also known to act as teratogens and abortifacients. Chronic ingestion of plants containing PAs has also led to cancer in experimental animals and metabolites of several PAs have been shown to be mutagenic in the Salmonella typhimurium/mammalian microsome system. However, no clinical association has yet been found between human cancer and exposure to PAs. Based on the extensive reports on the outcome of human exposure available in the literature, we conclude that while humans face the risk of veno-occlusive disease and childhood cirrhosis PAs are not carcinogenic to humans.     

武功山地区野生有毒植物资源研究

为了解武功山地区有毒植物资源情况及毒性特点,有效保护与利用武功山有毒植物资源,通过野外实地考察并结合查阅文献资料的方法,对该地区的有毒植物进行统计分析。结果显示,武功山地区共有有毒植物75科179属240种;形成以豆科(Leguminosae)、毛茛科(Ranunculaceae)、菊科(Asteraceae)、百合科(Liliaceae)4科为主的数量优势科(含10种及以上),以紫堇属(Corydalis)为主的数量优势属(含5种及以上)。该区有毒植物的生活习性以草本为主;以海拔400～499 m区域内的植物最多,且主要生长在山坡、林中、灌丛等环境中。区系地理成分复杂多样,科以泛热带分布和世界分布为主,属以北温带分布和泛热带分布为主,而种以中国特有分布和东亚分布最多。毒性以小毒为主,有毒部位以全株有毒为主;有毒化学成分颇为复杂,主要以生物碱为主,毒理类型以神经系统毒为主。     

Secondary transport as an efficient membrane transport mechanism for plant secondary metabolites

Plants produce a large number of secondary metabolites, such as alkaloids, terpenoids, and phenolic compounds. Secondary metabolites have various functions including protection against pathogens and UV light in plants, and have been used as natural medicines for humans utilizing their diverse biological activities. Many of these natural compounds are accumulated in a particular compartment such as vacuoles, and some are even translocated from source cells to sink organs via long distance transport. Both primary and secondary transporters are involved in such compartmentation and translocation, and many transporter genes, especially genes belonging to the multidrug and toxin extrusion type transporter family, which consists of 56 members in Arabidopsis, have been identified as responsible for the membrane transport of secondary metabolites. Better understandings of these transporters as well as the biosynthetic genes of secondary metabolites will be important for metabolic engineering aiming to increase the production of commercially valuable secondary metabolites in plant cells.     

Transfer of quinolizidine alkaloids from hosts to hemiparasites in two Castilleja-Lupinus associations: analysis of floral and vegetative tissues

Many hemiparasites, including several members of the Castilleja genus (Scrophulariaceae), obtain secondary compounds from their host plants. Both Castilleja miniata in subalpine Colorado and C. indivisa in central Texas have reduced herbivory when obtaining alkaloids from the hosts Lupinus argenteus and L. texensis (Fabaceae), respectively. However, pollinators were not deterred from visiting Castilleja parasitizing alkaloid-containing hosts. To determine if alkaloids are present in all tissues of plants parasitizing lupins, we analyzed floral tissue as well as leaves of both Castilleja species. Leaves, bracts, calices, corollas, gynoecium and nectar of both Castilleja species were examined for quinolizidine alkaloid presence using a Dragendorff reagent, and alkaloids were identified in vegetative tissue and nectar by capillary GLC and GLC-MS. Lupanine and alpha-isolupanine were the principal alkaloids in C. indivisa parasitizing L. texensis, while principal alkaloids of C. miniata parasitizing L. argenteus were 5,6-iso-dehydrolupanine, alpha-isolupanine, thermopsine, and 17-oxolupanine. Except for 17-oxolupanine, which was probably synthesized by biotransformation in the parasite, all other alkaloids correspond to those present in the host plants. Alkaloids were present in the leaves of both Castilleja species, and in the bracts, calices and gynoecium of some plants, but never in the corollas. Alkaloids from L. texensis and L. argenteus were not detected in nectar of either Castilleja species. The presence of alkaloids in leaves and outer floral tissue of both Castilleja species, but not nectar, may explain why alkaloid uptake and storage affected herbivores but not pollinators.     

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.     

Cytochromes P450 in the biosynthesis of glucosinolates and indole alkaloids

Characteristic of cruciferous plants is the synthesis of nitrogen- and sulfur-rich compounds, such as glucosinolates and indole alkaloids. The intact glucosinolates have limited biological activity, but give rise to an array of bio-active breakdown products when hydrolysed by endogenous β-thioglucosidases (myrosinases) upon tissue disruption. Both glucosinolates and indole alkaloids constitute an important part of the defence of plants against herbivores and pathogens, with the difference that a basal level of glucosinolates is ever-present in the plant whereas indole alkaloids are true phytoalexins that are de novo synthesised upon pathogen attack. With the completion of the genome sequence of the model plant, Arabidopsis thaliana, which is a crucifer, many genes involved in the biosynthesis of glucosinolates and indole alkaloids have been identified and cytochromes P450 are key players in these pathways. In the present review, we will focus on the cytochromes P450 in the biosynthesis of both groups of compounds. Their functional roles and regulation will be discussed.     

Diterpenoid alkaloids with chemotaxonomic significance from Aconitum spathulatum

Diterpenoid alkaloids have been acknowledged as of chemotaxonomic significance in plants from the genus Aconitum (Ranunculaceae). Phytochemical investigation on the Aconitum spathulatum W. T. Wang, an endemic Aconitum species in China, has led to the isolation of twelve C₁₉-diterpenoid alkaloids. The chemotaxonomic significance of these compounds are summarized.     

Alkaloid production in elicited cell suspension cultures of Erythrina americana Miller

A number of species of the genus Erythrina are rich in secondary metabolites, particularly phenolics and alkaloids that exhibit interesting anti-inflammatory, anti-plasmodial, bactericidal, curariform and fungicidal activities. Unfortunately, the isolation of these compounds through the extraction of organs and seeds of whole plants is becoming more difficult since the natural growing areas of many of the species, and particularly of Erythrina americana, are being urbanised. Plant tissue culture not only constitutes a viable method through which to preserve the species, but may also represent a constant and stable source of target alkaloids. Currently, however, in vitro systems, and especially cell suspension cultures, only accumulate low levels of the desired products. A number of strategies for increasing production have been proposed, the most successful of which involves elicitation of suspension cells with plant growth regulators. In this context, excellent results have been reported following elicitation of cell cultures derived from different species and genera with jasmonic acid and methyl jasmonate. The present paper provides a brief review of the novel approaches to the use of Erythrina alkaloids that have recently been described, and of the advances that have been made in the formation of tissue cultures of E. americana and their subsequent elicitation in attempts to augment alkaloid accumulation.