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Metabolomics and chemophenetics support the new taxonomy circumscription of two South America genera (Barnadesioideae, Asteraceae)
Abstract
Dasyphyllum Kunth is the most diverse genus of the South American subfamily Barnadesioideae (Asteraceae), comprising 31 species most of which are distributed along the Brazilian Atlantic Forest, Cerrado and Caatinga domains. The genus has traditionally been divided into two subgenera, namely Archidasyphyllum and Dasy-phyllum. However, recent phylogenetic, morphological, and biogeographical evidence led to a new circum-scription of Dasyphyllum by elevating the subgenus Archidasyphyllum to the generic rank. The present work aimed to explore a chemophenetic characterization of Dasyphyllum for further supporting its new circumscription by a metabolomic approach using liquid chromatography coupled to high resolution mass spectrometry and multi-variate statistical analyses. A total of 44 mass features were identified based on their UV spectra, high resolution MS data and MS2 fragmentation patterns as well as comparisons with standard compounds. Dasyphyllum samples exhibited a diversity of phenylpropanoids: 3-O-caffeoylquinic acid, 4-O-caffeoylquinic acid, 5-O-caffeoylquinic acid, 5-O-feruloylquinic acid, 5-O-caffeoylshikimic acid, 1,3-O-dicaffeoylquinic acid, 3,4-O-dicaffeoylquinic acid, 3,5-O-dicaffeoylquinic acid and 4,5-O-dicaffeoylquinic acid. On the other hand, Archidasyphyllum displayed the 2-O-caffeoyltartaric acid, 2,3-O-dicaffeoyltartaric acid and caffeoyl-feruloyltartaric acid as distinctive constituents. The occurrence of tartaric acid ester derivatives in Archidasyphyllum and its absence in Dasyphyllum may constitute a diagnostic chemical characteristic for further supporting the segregation of Archidasyphyllum from Dasyphyllum. The occurrence of phenylpropanoids in Archidasyphyllum and Dasyphyllum is here reported for the first time.
... Compounds 7, 10, and 11 showed the same Figure S14. Similarly, based on the chromatographic behavior and the similar fragmentation pathways, five other phenolic acid derivatives (peaks 15, 35, 64, 78, 84, and 96) were tentatively identified as protocatechuic acid, 4-hydroxybenzoic acid, 5-O-caffeoylshikimic acid, p-hydroxycinnamic acid, acteoside, and isoacteoside, respectively (Li et al., 2009;Ccana-Ccapatinta et al., 2020). The source of the nine quinic acids and derivatives was PC. ...
... Consequently, compound 37 (cryptochlorogenic acid), taken as an example, gave a quasi-molecular ion at m/z 353.0872 (C 16 H 17 O 9 Figure S15. Similarly, the remaining compounds (peaks 4, 20, 36, 46, 56, 59, and 61) were tentatively identified via comparison of their chromatographic retention times, exact molecular masses, and MS/MS spectra with those of literature data (Sun et al., 2016;Ccana-Ccapatinta et al., 2020). Detailed information on these compounds is summarized in Supplementary Tables S1 and S2. ...
The study of screening active constituents from traditional Chinese medicine (TCM) is important for explicating the mechanism of action of TCM and further evaluating the safety and efficacy effectively. However, detecting and identifying the active constituents from complicated biological samples still remain a challenge. Here, a practical, quick, and novel integrated strategy from in vitro, in situ, in vivo to in silico for rapidly screening the active constituents was developed. Firstly, the chemical profile of TCM in vitro was identified using UPLC-Q Exactive-Orbitrap HRMS. Secondly, the in situ intestinal perfusion with venous sampling (IPVS) method was used to investigate the intestinal absorption components. Thirdly, after intragastric administration of the TCM extract, the in vivo absorbed prototype components were detected and identified. Finally, the target network pharmacology approach was applied to explore the potential targets and possible mechanisms of the absorbed components from TCM. The reliability and availability of this approach was demonstrated using Tongfengding capsule (TFDC) as an example of herbal medicine. A total of 141 compounds were detected and identified in TFDC, and among them, 64 components were absorbed into the plasma. Then, a total of 35 absorbed bioactive components and 50 related targets shared commonly by compounds and gout were integrated via target network pharmacology analysis. Ultimately, the effects of the absorbed components on metabolism pathways were verified by experiments. These results demonstrated that this original method may provide a practical tool for screening bioactive compounds from TCM treating particular diseases. Furthermore, it also can clarify the potential mechanism of action of TCM and rationalize the application of TFDC as an effective herbal therapy for gout.
... Plant systematics has entered a new era with the rise of DNAsequencing, and the use of chemistry as single parameter to study phylogenetic relationships has been discontinued. The term "chemophenetic" has been proposed for studies aiming to describe the array of specialized metabolites of a given taxon, contributing to a phenetic chemical characterization of clades recently supported by DNAsequence based phylogeny (Ccana-Ccapatinta et al., 2020;Zidorn, 2019). The chemophenetic analysis of Solanum is based on evaluating the structural variability of steroidal alkaloids. ...
Steroidal alkaloids (SA) are nitrogen-containing specialized metabolites applied as chemophenetic markers in
Solanum L. (Solanaceae). Over time, Solanum has been the focus of several molecular phylogenetic studies in an
attempt to resolve its infrageneric classification and the relationship among species belonging to this genus. Here
we aimed to study SA chemodiversity to identify chemical patterns and to perform a chemophenetic characterization
of the Solanum genus and its major clades. Chemical literature data about Solanum steroidal alkaloids
was assessed and structural variability of this biogenetic group was used in the chemometric analysis, by
applying a Principal Component Analysis and Hierarchical Cluster Analysis. The results demonstrate that the SA
chemodiversity in Solanum is represented by the occurrence of nine SA subtypes. The biosynthetic predominance
of the spirosolane-type in Solanum clades was observed, except for the preference of the Potato clade in producing
the solanidane-type. The Geminata clade displayed low SA glycosylation patterns, containing 3-oxy
groups. In addition, low SA production in the Cyphomandra clade was observed. Chemical similarities between
the Archaesolanum, Dulcamaroid and Morelloid clades were observed by chemometric analyses. In sum,
chemophenetics was proven a reliable and additional tool to describe the array of specialized metabolites in
Solanum clades, showing chemical information suitable to corroborate molecular phylogenetic studies.
The species Spondias mombin and Spondias tuberosa are fruit plants from the family Anacardiaceae, and the fruits of these plants are popularly known as “cajá” and “umbu”, respectively, and are marketed as exotic fruits in Brazil. The promoted marketing of these species in the market is hampered by their genetic variability and a lack of knowledge of techniques for reproduction, harvesting, and conservation. Therefore, active germplasm banks (AGBs) were created by The Brazilian Agricultural Research Corporation (EMBRAPA) to conserve genetic resources and optimize the use of these species. One of the approaches to the selection of species is metabolomics studies. In this work, using liquid chromatography‒mass spectrometry-based metabolomics, multivariate statistical analysis was used to correlate the metabolomic profiles of the bark, branches, and leaves of S. mombin and S. tuberosa. Thus, the compounds that most influenced the observed groups were identified and indicated as chemical markers of these species. To carry out the dereplication of the metabolomic profiles, a library of chemical structures of the Anacardiaceae family was constructed, which enabled the identification of 40 compounds, 10 of which were at level 1 using the library and reference standards and 30 at level 2 using only the library. The results of the present study showed that the branches and bark contain gallic acid and citric acid as chemical markers, and their profiles are similar between species. In the case of the leaves of S. mombin, the anacardic acid C17:3 and quercetin derivatives were identified as chemical markers, while the leaves of S. tuberosa contained the anacardic acids C17:1, C17:2, and C13 as chemical markers. Meteorological factors had a greater influence on the metabolic profile of the leaves than did genetic variability. In the case of S. mombin leaves, flavonoids are inversely correlated with cloudiness and directly correlated with the temperature at the collection site.
Based on molecular phylogenetic studies, Barnadesioideae have been proposed to be the basal subfamily of Asteraceae. This is a complex of
10 genera and 87 species distributed primarily along the Andean mountains, Patagonia, and into southern Brazil and Uruguay. Phylogenetic
analyses have recovered all genera as monophyletic groups and have provided insights to their inter-relationships. Four generic clades have
been substantiated: (1) Chuquiraga, Doniophyton, and Duseniella; (2) Dasyphyllum; (3) Barnadesia and Huarpea; and (4) Archidasyphyllum,
Arnaldoa, and Fulcaldea. The remaining genus, the monospecific Schlechtendalia, has been an outlier in the subfamily, with some previous
analyses recovering it as basal for the entire subfamily, and others showing it as sister to Barnadesia and Huarpea (with weak support) as
well as to other genera. Recent massive sampling of loci has confirmed Schlechtendalia as the sister genus for the subfamily. Schlechtendalia
luzulifolia has morphology atypical for Asteraceae. The capitula are loose aggregations of florets, and the leaves are long and strap shaped,
more reminiscent of monocots. Morphological and anatomical investigations of the leaves reveal long, laminar blades with parallelodromous
vascularization. The vesture is often with ‘barnadesioid trichomes’, especially towards the base of the plant, plus additional uniseriate trichomes consisting of 3 to many cells, newly reported for the subfamily. Some glandular trichomes with 2-4 short cells also occur. The transverse
anatomy of the leaves reveals a single epidermal layer on both surfaces, which also contain the stomata (the leaf being amphistomatic). The
mesophyll is undifferentiated; the vascular traces are surrounded by sclerenchyma that not only encircles the traces but also extends towards
the epidermis and connects with it. The morphology and anatomy of the leaves of Schlechtendalia are divergent in comparison with other
genera of the subfamily. Chuquiraga, Doniophyton, and Huarpea have leaf adaptations for survival in xeric habitats, such as dense pubescence,
grey surfaces, and revolute margins. Schlechtendalia, in contrast, is adapted to a more mesic environment, especially near the Atlantic Ocean
and along the Uruguay and La Plata rivers. The leaves are oriented upright, which correlates with undifferentiated mesophyll and stomata
on both epidermal layers. The stem is an underground rhizome, an adaptation that permits survival during seasonal drought in the austral
summer in Uruguay and adjacent regions. It is hypothesized that Schlechtendalia may have become adapted to more mesic environments in
the Miocene prior to the rise of the Andes and development of the modern arid environments, into which many of the other genera of the
subfamily subsequently radiated.
Based on molecular phylogenetic studies, Barnadesioideae have been proposed to be the basal subfamily of Asteraceae. This is a complex of
10 genera and 87 species distributed primarily along the Andean mountains, Patagonia, and into southern Brazil and Uruguay. Phylogenetic
analyses have recovered all genera as monophyletic groups and have provided insights to their inter-relationships. Four generic clades have
been substantiated: (1) Chuquiraga, Doniophyton, and Duseniella; (2) Dasyphyllum; (3) Barnadesia and Huarpea; and (4) Archidasyphyllum,
Arnaldoa, and Fulcaldea. The remaining genus, the monospecific Schlechtendalia, has been an outlier in the subfamily, with some previous
analyses recovering it as basal for the entire subfamily, and others showing it as sister to Barnadesia and Huarpea (with weak support) as
well as to other genera. Recent massive sampling of loci has confirmed Schlechtendalia as the sister genus for the subfamily. Schlechtendalia
luzulifolia has morphology atypical for Asteraceae. The capitula are loose aggregations of florets, and the leaves are long and strap shaped,
more reminiscent of monocots. Morphological and anatomical investigations of the leaves reveal long, laminar blades with parallelodromous
vascularization. The vesture is often with ‘barnadesioid trichomes’, especially towards the base of the plant, plus additional uniseriate trichomes consisting of 3 to many cells, newly reported for the subfamily. Some glandular trichomes with 2-4 short cells also occur. The transverse
anatomy of the leaves reveals a single epidermal layer on both surfaces, which also contain the stomata (the leaf being amphistomatic). The
mesophyll is undifferentiated; the vascular traces are surrounded by sclerenchyma that not only encircles the traces but also extends towards
the epidermis and connects with it. The morphology and anatomy of the leaves of Schlechtendalia are divergent in comparison with other
genera of the subfamily. Chuquiraga, Doniophyton, and Huarpea have leaf adaptations for survival in xeric habitats, such as dense pubescence,
grey surfaces, and revolute margins. Schlechtendalia, in contrast, is adapted to a more mesic environment, especially near the Atlantic Ocean
and along the Uruguay and La Plata rivers. The leaves are oriented upright, which correlates with undifferentiated mesophyll and stomata
on both epidermal layers. The stem is an underground rhizome, an adaptation that permits survival during seasonal drought in the austral
summer in Uruguay and adjacent regions. It is hypothesized that Schlechtendalia may have become adapted to more mesic environments in
the Miocene prior to the rise of the Andes and development of the modern arid environments, into which many of the other genera of the
subfamily subsequently radiated.
Coffee ( Coffea spp) has evolved from an agricultural commodity to a specialty beverage, regarding the product’s trading, appreciation, philosophies, and purposes of consumption. Consequently, part of the coffee industry has focused on the sensory complexion and high-quality to meet engaged consumers. To evaluate the chemical profiles and distinctiveness of natural products from plants, metabolomics has emerged as a valuable tool. In this work, we carried out an untargeted metabolomic approach based on reversed-phase liquid chromatography coupled with mass spectrometry, followed by multivariate statistical analysis to obtain the metabolic fingerprints of 21 coffee samples belonging to two species and five botanical varieties, as follows: C. arabica (var. yellow catuai , yellow bourbon , and yellow obata ) and C. canephora (var. conilon , and robusta ). The samples were obtained in the 2022 Edition of the “Brazilian International Conference of Coffee Tasters”, state of Rondônia, Brazil. Principal Component Analysis and Orthogonal Projections Latent Structures Discriminant Analysis were performed using the metabolomic data, resulting in the discrimination of coffee samples based on their chemical profiles. Caffeine, DIMBOA-Gl, roemerine, and cajanin were determined as chemical markers for C. canephora samples, and toralactone, cnidilide, LysoPC(18:2(9Z,12Z)), Lysophosphatidylcholine(16:0/0:0), and 2,3-Dehydrosilybin for C. arabica samples. In addition to the genetic variability, our results show the possible influence of a terroir factor in the production of secondary metabolites of coffee samples, mainly for individuals of C. canephora .
Simple Summary
Modern evolutionary biology offers a wide variety of methods to explore the evolution of species and to describe their relationships. The methods of DNA/RNA sequence analysis have been developing for decades and have become increasingly popular and reasonably reliable. Nevertheless, final phylogenetic trees for many taxa are still under debate because both classical and genomics-based approaches have their own limitations for phylogenetic tree reconstruction. Here, we propose the use of younger ‘omics’ methods, namely quantitative metabolomics, to aid the phylogeny reconstruction of vertebrates. We show that metabolomics-based hierarchical clustering analysis trees match, although not perfectly, to the genomics-based trees.
Abstract
In the current pilot study, we propose the use of quantitative metabolomics to reconstruct the phylogeny of vertebrates, namely birds. We determined the concentrations of the 67 most abundant metabolites in the eye lenses of the following 14 species from 6 orders of the class Aves (Birds): the Black kite (Milvus migrans), Eurasian magpie (Pica pica), Northern raven (Corvus corax), Eurasian coot (Fulica atra), Godlewski’s bunting (Emberiza godlewskii), Great crested grebe (Podiceps cristatus), Great tit (Parus major), Hawfinch (Coccothraustes coccothraustes), Hooded crow (Corvus cornix), House sparrow (Passer domesticus), Rock dove (Columba livia), Rook (Corvus frugilegus), Short-eared owl (Asio flammeus) and Ural owl (Strix uralensis). Further analysis shows that the statistical approaches generally used in metabolomics can be applied for differentiation between species, and the most fruitful results were obtained with hierarchical clustering analysis (HCA). We observed the grouping of conspecific samples independently of the sampling place and date. The HCA tree structure supports the key role of genomics in the formation of the lens metabolome, but it also indicates the influence of the species lifestyle. A combination of genomics-based and metabolomics-based phylogeny could potentially resolve arising issues and yield a more reliable tree of life.
The family Bromeliaceae Juss. is a large one, with 78 genera and 3659 species. Ananas is considered the most important genus from an economic perspective, and Brazil ranks third worldwide in the production of pineapple. Fruits of Ananas comosus (L.) Merril.) are most consumed and are widely appreciated all over the world. However, the chemical profile of its leaves and the potential for the production of secondary metabolites have been little explored. Further, the taxonomy of the genus is constantly revised due to the agricultural profile of the genus. In this work, for the first time, we carried out an untargeted metabolomic approach based on liquid chromatography coupled with mass spectrometry, followed by multivariate statistical analysis to obtain the metabolic fingerprints of 35 leaf samples of individuals belonging to the two species of Ananas (A. comosus and A. macrodontes) and five botanical varieties of A. comosus (var. microstachys, bracteatus, comosus, erectifolius, and parguazensis) from the Pineapple Active Germplasm Bank, located at Embrapa Cassava and Fruits, Brazilian Agricultural Research Corporation, Brazil. The metabolomic data of the 35 samples and their taxonomic information were combined to characterize the genus based on the chemical profile of the species and varieties, and, for the first time in the literature, 46 substances were annotated in the two species. Based on multivariate statistical analysis by Principal Component Analysis and Orthogonal Projections Latent Structures Discriminant Analysis using the metabolomic data, it was possible to discriminate among the species and varieties based on their chemical profiles. Our results show that the chemical composition of Ananas leaves can be used to assist in taxonomic identification.
Dasyphyllum Kunth is the most diverse genus of the South American subfamily Barnadesioideae (Asteraceae), comprising 33 species that occur in tropical Andes, Atlantic Forest, Caatinga, Cerrado, and Chaco. Based on distribution, variation in anther apical appendages, and leaf venation pattern, it has traditionally been divided into two subgenera, namely, Archidasyphyllum and Dasyphyllum. Further, based on involucre size and capitula arrangement, two sections have been recognized within subgenus Dasyphyllum: Macrocephala and Microcephala (=Dasyphyllum). Here, we report a phylogenetic analysis performed to test the monophyly of Dasyphyllum and its infrageneric classification based on molecular data from three non-coding regions (trnL-trnF, psbA-trnH, and ITS), using a broad taxonomic sampling of Dasyphyllum and representatives of all nine genera of Barnadesioideae. Moreover, we used a phylogenetic framework to investigate the evolution of the morphological characters traditionally used to recognize its infrageneric groups. Our results show that neither Dasyphyllum nor its infrageneric classification are currently monophyletic. Based on phylogenetic, morphological, and biogeographical evidence, we propose a new circumscription for Dasyphyllum, elevating subgenus Archidasyphyllum to generic rank and doing away with the infrageneric classification. Ancestral states reconstruction shows that the ancestor of Dasyphyllum probably had acrodromous leaf venation, bifid anther apical appendages, involucres up to 18 mm in length, and capitula arranged in synflorescence.
Dasyphyllum sect. Macrocephala is restricted to the Cerrado, Caatinga, and Atlantic Forest biomes of Brazil, spreading into similar areas in Bolivia and Paraguay. The six recognized species in this section are monoecious shrubs with erect or decumbent branches, single or paired, rarely fasciculate, straight or curved axillary spines, leaves with apiculate or aristate apices, 5-7 basally or suprabasally acrodromous veins, sessile capitula, usually solitary or in groups of two to four, a campanulate or infundibuliform involucre generally longer than 20 mm, and with hermaphroditic florets usually with liguliform corollas and externally sericeous lobes. An identification key, descriptions, comments regarding morphology and taxonomy, maps showing geographical distribution, and illustrations are presented, together with 17 new synonyms and 18 typifications.
The subfamily Barnadesioideae (Asteraceae) constitutes a group of spiny plants that are entirely restricted to South America and currently encompasses 92 species distributed in nine genera. Barnadesioideae is particularly interesting because this subfamily constitutes the sister group of all other Asteraceae, and provides insights into the early evolution of Asteraceae. The present work summarizes the current knowledge of the chemistry and medicinal uses of Barnadesioideae. The up-to-date phytochemical profile of Barnadesioideae is composed of phenolic compounds, flavonoids, and triterpenoids, representing 39 different compounds described in 45 species of the subfamily. The presumable absence of sesquiterpene lactones—the typical Asteraceae taxonomical markers—in members of Barnadesioideae is also discussed. A few members of the genera Barnadesia, Dasyphyllum, and more frequently, Chuquiraga, are reported in the traditional medicine of Argentina, Brazil, Bolivia, Chile, Colombia, Ecuador, and Peru, where they are known for their antitussive, expectorant, anti-inflammatory, and many other properties. Chuquiraga jussieui, Chuquiraga spinosa, and Chuquiraga weberbaueri are species frequently sold in medicinal plant markets of Ecuador and Peru, where they are commonly recommended for the relief of genitourinary and reproductive disorders in women and men. Some phytopharmaceuticals containing C. spinosa are also marketed in Europe and North America. Further phytochemical studies on the members of Barnadesioideae would be of great interest for the chemotaxonomy of the family Asteraceae. Moreover, profiling the phytochemical composition of those medically important Barnadesioideae would support their uses in traditional medicine.
Chemotaxonomy and the comparative analysis of metabolic features of fungi have the potential to provide valuable information relating to ecology and evolution, but have not been fully explored in fungal biology. Here, we investigated the chemical diversity of legume-associated Ascochyta and Phoma species and the possible use of a metabolomics approach using liquid chromatography-mass spectrometry for their classification. The metabolic features of 45 strains including 11 known species isolated from various legumes were extracted, and the datasets were analyzed using chemometrics methods such as principal component and hierarchical clustering analyses. We found a high degree of intra-species consistency in metabolic profiles, but inter-species diversity was high. Molecular phylogenies of the legume-associated Ascochyta/Phoma species were estimated using sequence data from three protein-coding genes and the five major chemical groups that were detected in the hierarchical clustering analysis were mapped to the phylogeny. Clusters based on similarity of metabolic features were largely congruent with the species phylogeny. These results indicated that evolutionarily distinct fungal lineages have diversified their metabolic capacities as they have evolved independently. This whole metabolomics approach may be an effective tool for chemotaxonomy of fungal taxa lacking information on their metabolic content.
Cyclooxygenase and 5-lipoxygenase are enzymes that catalyze important inflammatory pathways, suggesting that dual cyclooxygenase/lipoxygenase inhibitors should be more efficacious as anti-inflammatory medicines with lower side effects than the currently available nonsteroidal anti-inflammatory drugs. Many plants from the family Asteraceae have anti-inflammatory activities, which could be exerted by inhibiting the cyclooxygenase-1 and 5-lipoxygenase enzymes. Nevertheless, only a small number of compounds from this family have been directly evaluated for their ability to inhibit the enzymes in cell-free assays. Therefore, this study systematically evaluated 57 Asteraceae extracts in vitro in enzyme activity experiments to determine whether any of these extracts exhibit dual inhibition of cyclooxygenase-1 and 5-lipoxygenase. The chemical profiles of the extracts were obtained by the high-performance liquid chromatography-ultraviolet-diode array detector method, and their major constituents were dereplicated. Of the 57 tested extracts, 13 (26.6 %, IC50 range from 0.03-36.2 µg/mL) of them displayed dual inhibition. Extracts from known anti-inflammatory herbs, food plants, and previously uninvestigated species are among the most active. Additionally, the extract action was found to be specific with IC50 values close to or below those of the standard inhibitors. Thus, the active extracts and active substances of these species are potent inhibitors acting through the mechanism of dual inhibition of cyclooxygenase-1 and 5-lipoxygenase. The extracts were prepared for this study using nontoxic extraction solvents (EtOH-H2O), requiring only a small amount of plant material to carry out the bioassays and the phytochemical analyses. In summary, this study demonstrated the potential of the investigated species as dual inhibitors, revealing their potential as pharmaceuticals or nutraceuticals.
Georg Thieme Verlag KG Stuttgart · New York.
The taxonomic classification of the genus Vernonia Schreb is complex and, as yet, unclear. We here report the use of untargeted metabolomics approaches, followed by multivariate analyses methods and a phytochemical characterization of ten Vernonia species. Metabolic fingerprints were obtained by accurate mass measurements and used to determine the phytochemical similarities and differences between species through multivariate analyses approaches. Principal component analysis based on the relative levels of 528 metabolites, indicated that the ten species could be clustered into four groups. Thereby, V. polyanthes was the only species with presence of flavones chrysoeriol-7-O-glycuronyl, acacetin-7-O-glycuronyl and sesquiterpenes lactones piptocarphin A and piptocarphin B, while glaucolide A was detected in both V. brasiliana and V. polyanthes, separating these species from the two other species of the Vernonanthura group. Species from the Lessingianthus group were unique in showing a positive response in the foam test, suggesting the presence of saponins, which could be confirmed by metabolite annotation. V. rufogrisea showed a great variety of sesquiterpene lactones, placing this species into a separate group. Species within the Chrysolaena group were unique in accumulating clovamide. Our results of LC-MS-based profiling combined with multivariate analyses suggest that metabolomics approaches, such as untargeted LC-MS, may be potentially used as a large-scale chemotaxonomical tool, in addition to classical morphological and cytotaxonomical approaches, in order to facilitate taxonomical classifications.
Metabolomics is still faced with several significant challenges which currently limit its full scientific potential. The identification of metabolites is essential to convert analytical data into meaningful biological knowledge. However, identification confidence can vary widely because the process of identification is complex and dependent on the analytical platform and robustness of the methods applied, as well as the databases and resources used. Confident and unequivocal structure identification requires significant effort, which is multiplied dramatically in non-targeted metabolomics studies where 10–100s of metabolites can be deemed as biologically important and require identification. Mass spectrometry (MS), nuclear magnetic resonance spectroscopy (NMR) or integrated MS–NMR strategies (Dunn et al. 2013; Kind and Fiehn 2010; van der Hooft et al. 2011) provide much information for the identification of metabolites (e.g. 1D/2D-NMR and MS/MS).
There is a general consensus that supports the need for standardized reporting of metadata or information describing large-scale metabolomics and other functional genomics data sets. Reporting of standard metadata provides a biological and empirical context for the data, facilitates experimental replication, and enables the re-interrogation and comparison of data by others. Accordingly, the Metabolomics Standards Initiative is building a general consensus concerning the minimum reporting standards for metabolomics experiments of which the Chemical Analysis Working Group (CAWG) is a member of this community effort. This article proposes the minimum reporting standards related to the chemical analysis aspects of metabolomics experiments including: sample preparation, experimental analysis, quality control, metabolite identification, and data pre-processing. These minimum standards currently focus mostly upon mass spectrometry and nuclear magnetic resonance spectroscopy due to the popularity of these techniques in metabolomics. However, additional input concerning other techniques is welcomed and can be provided via the CAWG on-line discussion forum at http://msi-workgroups.sourceforge.net/ or http://Msi-workgroups-feedback@lists.sourceforge.net. Further, community input related to this document can also be provided via this electronic forum.
Medicinal plant use has persisted as a long standing tradition in the Mapuche communities of Southern Argentina and Chile. An ethnobotanical survey was conducted in the rural Curruhuinca community located near the mountain city of San Martin de los Andes, Argentina. Semi-structured interviews were carried out on 22 families in order to examine the present use of medicinal plants and their reputed therapeutic effects. Ecological variables, such as distance to the gathering site and biogeographical origin were also analyzed. Our results showed that the Curruhuinca dwellers cited 89 plant species for medicinal purposes, both of native and exotic origin. They know about 47 native plants, of which they use 40, and they know of 42 exotic medicinal plants of which they use 34. A differential pattern was observed given that only native species, relevant for the traditional Mapuche medicine, were collected at more distant gathering sites. The interviewees mentioned 268 plant usages. Those most frequently reported had therapeutic value for treating digestive ailments (33%), as analgesic/anti-inflammatory (25%) and antitusive (13%). Native species were mainly cited as analgesics, and for gynecological, urinary and "cultural syndrome" effects, whereas exotic species were mainly cited for digestive ailments. The total number of medicinal plants known and used by the interviewees was positively correlated with people's age, indicating that this ancient knowledge tends to disappear in the younger generations.
The tea prepared from leaves and thorns of Dasyphyllum brasiliensis (Asteraceae) is used in the traditional medicine in Brazil for the treatment of oral and oropharyngeal diseases. In this study, we investigated the anti-inflammatory activity of this plant. The aqueous crude extract (ACE), the methanol-water (MeOH-H(2)O) fraction obtained by solvent partition and its fractionation products were evaluated for their anti-inflammatory activities on acute peritonitis induced by beta-glucan from the cell walls of Histoplasma capsulatum. The antiedematogenic activity was also tested using the carrageenan-induced paw edema assay in mice. Oral administration of 100 and 300mg/kg of the ACE in mice caused a significant reduction of neutrophil and eosinophil recruitment in the acute peritonitis assay. In addition, ACE at 300mg/kg inhibited the number of mononuclear cells recruitment. The MeOH-H(2)O fraction and its fractionation products (all at 100mg/kg) also presented anti-inflammatory activities, confirmed by the inhibition of cells recruited to the peritoneal cavity. ACE at 100mg/kg did not show any significant reduction of the edema in the mice paw injected with carrageenan. These data together suggest that Dasyphyllum brasiliensis presents significant anti-inflammatory activity, thus supporting the popular use of the tea in the treatment of inflammatory diseases.
The aromatic pink-flowered Phebalium complex is comprised by P. nottii Maiden & Betche, P. speciosum I. Telford and the very similar but mostly white-flowered P. woombye (F.M.Bailey) Domin. Phebalium nottii, as currently circumscribed, includes several geographically disjunct populations that have been segregated at the N.C.W. Beadle Herbarium as putatively distinct species, several of high conservation value. To study volatiles sustainably , large-scale hydrodistillation was aborted and only single leaves were removed from herbarium vouchers, extracted into solvent and analysed by GC-MS. Unlike other species of Phebalium, volatiles in pink-flowered Phebalium are mostly dominated by spathulenol and bicyclogermacrene. Multivariate analysis of the chemistry of volatiles clearly demonstrated good agreement between chemotypes and putative taxa in central Queensland populations. Southern taxa, and the true P. nottii sensu stricto from northern Queensland, express high levels of volatile coumarins. Thus, morphological relationships are mostly reflected in morphometric clusters. As with other members of Phebalium, most taxa can be distinguished on chemistry alone, using only GC-MS analysis of herbarium material. These results corroborate several new species and reveal relationships within the heterogeneous species aggregate of P. nottii.
The phytochemical composition of Arnaldoa species is barely known. In this work, the occurrence of caffeic acid ester derivatives and flavonoids in A. argentea, A. macbrideana and A. weberbaueri was established by liquid chromatography associated to high-resolution mass spectrometry analyses and comparison with data from isolated compounds. The distribution of chlorogenic acids in the genus Arnaldoa is herein described for the first time. The metabolite profile of Arnaldoa species was compared to that of Tithonia diversifolia, a known and rich source of chlorogenic acids and sesquiterpene lactones. In addition to the mono-and dicaffeoyl quinic acids present in T. diversifolia, Arnaldoa species exhibited the mono-and dicaffeoyl tartaric acids. Furthermore, mass features correspondent to that of sesquiterpene lactones present in T. diversifolia were not observed in Arnaldoa species. The chemotaxonomic implications of caffeic acid ester derivatives and flavonoid glycosides, as well as the potential absence of sesquiterpene lactones in the genus Arnaldoa and subfamily Barnadesioideae are discussed .
Plant chemosystematic or chemotaxonomic studies based purely on the profiles of small molecules have become obsolete as tools to study phylogenetic relationships of higher plants due to the advent of the much more powerful (macro-)molecular techniques and new methods of data analysis established in parallel to these techniques. A new term is herein proposed for the field of studies aimed at the exploitation of characteristic arrays of specialized natural products of plant taxa: plant chemophenetics. Chemophenetic studies as defined here are studies aimed at describing the array of specialized secondary metabolites in a given taxon. Thus, chemophenetic studies contribute to the phenetic description of taxa, similar to anatomical, morphological, and karyological approaches, which have already been recognized as of major importance for establishing "natural" systems, and which continue to be of the utmost importance for the description of organisms classified with the help of modern molecular methods.
Vernonia sensu lato is the largest and most complex genus of the tribe Vernonieae (Asteraceae). The tribe is chemically characterized by the presence of sesquiterpene lactones and flavonoids. Over the years, several taxonomic classifications have been proposed for Vernonia s.l. and for the tribe; however, there has been no consensus among the researches. According to traditional classification, Vernonia s.l. comprises more than 1000 species divided into sections, subsections and series (sensu Bentham). In a more recent classification, these species have been segregated into other genera and some subtribes were proposed, while the genus Vernonia sensu stricto was restricted to 22 species distributed mainly in North America (sensu Robinson). In this study, species from the subtribes Vernoniinae, Lepidaploinae and Rolandrinae were analyzed by UHPLC-UV-HRMS followed by multivariate statistical analysis. Data mining was performed using unsupervised (HCA and PCA) and supervised methods (OPLS-DA). The HCA showed the segregation of the species into four main groups. Comparing the HCA with taxonomical classifications of Vernonieae, we observed that the groups of the dendogram, based on metabolic profiling, were in accordance with the generic classification proposed by Robinson and with previous phylogenetic studies. The species of the genera Stenocephalum, Stilpnopappus, Strophopappus and Rolandra (Group 1) were revealed to be more related to the species of the genus Vernonanthura (Group 2), while the genera Cyrtocymura, Chrysolaena and Echinocoryne (Group 3) were chemically more similar to the genera Lessingianthus and Lepidaploa (Group 4). These findings indicated that the subtribes Vernoniinae and Lepidaploinae are non-chemically homogeneous groups and highlighted the application of untargeted metabolomic tools for taxonomy and as indicators of species evolution. Discriminant compounds for the groups obtained by OPLS-DA were determined. Groups 1 and 2 were characterized by the presence of 3',4'-dimethoxyluteolin, glaucolide A and 8-tigloyloxyglaucolide A. The species of Groups 3 and 4 were characterized by the presence of putative acacetin 7-O-rutinoside and glaucolide B. Therefore, untargeted metabolomic approach combined with multivariate statistical analysis, as proposed herein, allowed the identification of potential chemotaxonomic markers, helping in the taxonomic classifications.
Sixteen compounds including dihydroxy prenylfuranocoumarins/3-hydroxy-3-methylglutaric acid conjugates and dihydroxy prenylfuranocoumarins/3-hydroxy-3-methylglutaric acid/1-O-flavonyl-β-d-glucopyranoside conjugates, together with other dihydroxyprenylfuranocoumarins conjugates, were isolated from the ethyl acetate extract of the fruit peels of Citrus hystrix. Some of the isolates were evaluated for their cholinesterase inhibitory activity, but only one compound possessing a 3-O-β-d-glucopyranosyl-3,5,7,4′-tetrahydroxy-6,8,3′-trimethoxyflavonol nucleus in the prenylfuranocoumarin–HMGA conjugate showed strong activity.
Dasyphyllum diamantinense is a new species endemic to the Chapada Diamantina Mountains in the northern section of the Espinhaço Range, in Bahia State, Brazil, which grows in rocky fields, forests and savannas, and on inselbergs. The new taxon is morphologically similar to Dasyphyllum leptacanthum. Affinities and diagnostic characters are discussed, and illustrations and a map are provided.
The flavonoid profiles of some species of the following genera of the Barnadesioideae (Asteraceae) consist of mono- and diglycosides of kaempferol and quercetin: Arnaldoa, Barnadesia, Chuquiraga, Dasyphyllum, Doniophyton, Fulcaldea, and Schlechtendalia. These South American genera previously comprised part of the subtribe Barnadesiinae of Mutisieae. Very simple flavonoid profiles were also noted for the Chilean monotypic Gypothamnium and the Hawaiian endemic Hesperomannia arborescens of subtribe Mutisiinae. The simple flavonoid profiles of the barnadesioid genera are taken as further evidence for the primitive status of this subfamily as suggested by the absence of a 22kb cpDNA inversion in this group of genera. Preliminary studies of the flavonoids of the Calyceraceae have shown that the pigment profile of species of Acicarpha and Gamocarpha are very similar to the profile seen in the barnadesioid genera. A brief discussion of relationships between Barnadesioideae and Acicarpha as a possible representative of the prototypical Calyceraceae, indicated by floral development, diploid chromosome number, geography, and flavonoid chemistry, is included.
Solanum somalense leaves, used in Djibouti for their medicinal properties, were extracted by MeOH. Because of the high polyphenol and flavonoid contents of the extract, respectively determined at 80.80 ± 2.13 mg gallic acid equivalent/g dry weight and 24.4 ± 1.01 mg quercetin equivalent/g dry weight, the isolation and purification of the main polyphenols were carried out by silica gel column chromatography and centrifugal partition chromatography. Column chromatography led to 11 enriched fractions requiring further purification, while centrifugal partition chromatography allowed the easy recovery of the main compound of the extract. In a solvent system composed of CHCl3 /MeOH/H2 O (9.5:10:5), 21.8 mg of this compound at 97% purity were obtained leading to a yield of 2.63%. Its structure was established as 5-O-caffeoylshikimic acid by mass spectrometry and NMR spectroscopy. This work shows that S. somalense leaves contain very high level of 5-O-caffeoylshikimic acid (0.74% dry weight), making it a potential source of production of this secondary metabolite that is not commonly found in nature but could be partly responsible of the medicinal properties of S. somalense leaves. This article is protected by copyright. All rights reserved.
Advances in high-throughput, comprehensive small molecule analytical techniques have seen the development of the field of metabolomics. The coupling of mass spectrometry with high-resolution chromatography provides extensive chemical profiles from complex biological extracts. These profiles include thousands of compounds linked to gene expression, and can be used as taxonomic characters. Studies have shown metabolite profiles to be taxon specific in a range of organisms, but few have investigated taxonomically problematic plant taxa. This study used a phenetic analysis of metabolite profiles to test taxonomic boundaries in the Olearia phlogopappa (Asteraceae) complex as delimited by morphological data. Metabolite profiles were generated from both field- and shade house-grown material, using liquid chromatography-mass spectrometry (LC-MS). Aligned profiles of 51 samples from 12 taxa gave a final dataset of over 10,000 features. Multivariate analyses of field and shade house material gave congruent results, both confirming the distinctiveness of the morphologically defined species and subspecies in this complex. Metabolomics has great potential in alpha taxonomy, especially for testing the boundaries of closely related taxa where DNA sequence data has been uninformative.
Ethnopharmacological relevance:
Empacho is one of the most recognized cultural-bound syndromes in Argentina. It is a digestive disorder with many causes, being excessive food intake the most frequent. It is easily diagnosed in household medicine and there are different treatments applied for releasing the obstruction of the gastrointestinal tract. Therapeutics includes the use of medicinal plants and abdominal maneuvers, as well as rituals of magical and/or religious nature. The aim of this work is to analyze the compiled literature, considering documents from the XVIIIth century up to present, related to the employed plant species for the treatment of empacho.
Material and methods:
The bibliographic and journal collections of several Argentinean and foreign libraries and bookstores were consulted, in addition to the comprehensive review of the specific information found online.
Results:
Ninety (90) primary sources, spanning three hundred years (from 1710 to 2010) were found; most of them included ethnobotanical studies besides others of medical botany, pharmacobotanical and anthropological origin. A total of 152 plant species used to treat empacho were found in 360 total quotations, being Dysphania ambrosioides (L.) Mosyakin and Clemants; Alternanthera pungens Kunth; Ruta chalepensis L.; Clinopodium gilliesii (Benth.) Kuntze; Aloysia polystachya (Griseb.) Moldenke; Lippia turbinata Griseb., and Pluchea sagittalis (Lam.) Cabrera, the most frequently mentioned. The main therapeutic properties of the medicinal plants cited against empacho are stomachic, purgative, antispasmodic, bitter-tonic, carminative, and cholagogue-choleretic.
Conclusions:
The variety of regions - spanning most of the country - from which the information comes, as well as the great variety of therapeutic strategies used, diversity of plant species and knowledge related to the treatment of empacho, is directly associated with the great significance that this disorder has within the system of medical-nosologic representations of the Argentinean popular medicine.
Web services, as an aspect of cloud computing, are becoming an important part of the general IT infrastructure, and scientific computing is no exception to this trend. We propose a simple approach to develop chemical web services, through which servers could expose the essential data manipulation functionality that students and researchers need for chemical calculations. These services return their results as JSON (JavaScript Object Notation) objects, which facilitates their use for web applications. The ChemCalc project demonstrates this approach: we present 3 web services related with mass spectrometry, namely isotopic distribution simulation, peptide fragmentation simulation and molecular formula determination. We also developed a complete web application based on these 3 web services, taking advantage of modern HTML5 and JavaScript libraries (ChemDoodle and jQuery).
The fragmentation behavior of all six dicaffeoylquinic acids (diCQA) has been investigated using LC-MS(4). It is possible to discriminate between each of the isomers including those for which commercial standards are not available. For diCQA, the ease of removal of the caffeoyl residue during fragmentation is 1 approximately = 5 > 3 > 4. The distinctive fragmentation observed for the little-studied 1,4-dicaffeoylquinic acid involves elimination of the C1 caffeoyl residue, repeated dehydrations leading to the aromatization of the quinic acid moiety, and its decarboxylation. It is suggested that this process is initiated by the C1 carboxyl protonating the C5 hydroxyl in the inverted chair conformer, followed by its protonating the C1 caffeoyl residue in the favored chair conformation. The fragmentation of 1-caffeoylquinic acid is indistinguishable from that of the commercially available 5-caffeoylquinic acid, but these two isomers can be distinguished easily by their facile chromatographic resolution on reversed phase packings. The hierarchical key previously developed for characterizing chlorogenic acids has been extended to accommodate 1-caffeoylquinic acid and the 1-acyl dicaffeoylquinic acids.
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