Glaucolides and related sesquiterpene lactones from Vernonia chamaedrys

Catalán, César A.N.; Iglesias, Dora I. A. de; Kavka, J.; Sosa, Virginia E.; Herz, Werner

doi:10.1016/0031-9422(88)80613-7

Cited by 21 publications

(21 citation statements)

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“…This finding suggested an absence of the characteristic glaucolide‐type C‐10 ester group in peak VI structure. Thus, peak VI was characterized as stilpnotomentolide‐8‐ O ‐methylacrylate (glaucolide derivative), taking into consideration its tandem mass data and the chemotaxonomy of the tribe as this metabolite was previously obtained from Vernonanthura chamaedrys …”

Section: Resultsmentioning

confidence: 99%

ESI‐QTof‐MS characterization of hirsutinolide and glaucolide sesquiterpene lactones: Fragmentation mechanisms and differentiation based on Na⁺/H⁺ adducts interactions in complex mixture

et al. 2019

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Sesquiterpene lactones (SL) have been reported with various biological effects.Among the described SL skeletons, hirsutinolide and glaucolide have not been extensively studied by mass spectrometry (MS), especially how to distinguish them in organic matrices. Thus, this paper reports (1) a strategy of their differentiation based on MS behavior during the ionization and (2) a proposal of the fragmentation pattern for both SL-subtypes. ESI(+)-HRMS data of four isolated SL (hirsutinolides 1 and 3; glaucolides 2 and 4) were recorded by direct and UPLC water-sample combined injections. These analyses revealed that hirsutinolides and glaucolides formed [M+Na] + ion during the operation of the direct MS injection, and ([M+Na] + and [M+H-H 2 O] + ) and[M+H] + ions were respectively observed for hirsutinolides and glaucolides during the operation of combined UPLC water and sample MS injection. Computational simulations showed that the complex hirsutinolide (1)-Na + formed with a lower preparation energy compared with the complex glaucolide (2)-Na + . However, despite their different behavior during the ionization process, ESI(+)-HRMS/MS analyses of 1-4 gave similar fragmentation patterns at m/z 277, 259, 241, and 231 that can be used as diagnostic ions for both skeletons. Moreover, the differentiation strategy based on the nature of the complex SL-adducts and their MS/MS fragmentation pattern were successfully applied for the chemical characterization of the extract from Vernonanthura tweedieana using UPLC-ESI-HRMS/MS. Among the characterized metabolites, SL with hirsutinolide and glaucolide skeletons showed the aforementioned diagnostic fragments and an ionization behavior that was similar to those observed during the water-sample combined injection. KEYWORDShirsutinolides and glaucolides, ESI-QTofMS n analysis, ESI adducts interaction, fragmentation mechanism, computational study Correction added on 22 May 2020, after online publication: the data in Tables 1, 2, 3, 5 and the citation numbering throughout the article were corrected post publication. /journal/jms 915 916 DA SILVA ET AL. Journal of MASS SPECTROMETRY RESULTS AND DISCUSSION ESI-HRMS/MS analysis of pure compoundsAs depicted in Table 1, ESI(+)-HRMS analysis by direct injection indicated that the SL 1-4 afforded as base peak the ions at m/z 445.1473 (1), m/z 487.1570 (2), m/z 419.1327 (3), and m/z 461.1422 (4), corresponding to [M+Na] + and suggesting a strong affinity for Na + . Moreover, protonated ions [M+H] + were not detected for the hirsutinolide skeletons ( compounds 1 and 3), whereas [M+H] + ions were observed in extremely low abundance for glaucolides 2 (m/z 465.1740, 15%) and 4 (m/z 439.1620, 2%).DA SILVA ET AL.

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Section: Resultsmentioning

confidence: 99%

ESI‐QTof‐MS characterization of hirsutinolide and glaucolide sesquiterpene lactones: Fragmentation mechanisms and differentiation based on Na⁺/H⁺ adducts interactions in complex mixture

et al. 2019

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“…The extensive comparison of 1 H-NMR data of 1 and 2 revealed that the coupling constants of H-8 with H-9 were significantly different, suggesting that compound 2 wasa C-8 stereoisomer of 1. In the case of H-10b as in 1, the coupling constant of J 8,9 usually amounted to 6.0 ± 8.0 Hz [2], [12], [13], [14], [15] while the J 8,9 of 2 showed 10.7Hz. The stereochemistry of 2 was further confirmed by its NOESY spectrum.…”

Section: Resultsmentioning

confidence: 95%

Sesquiterpene Lactones with Potent Cytotoxic Activities fromVernonia chinensis

Chen¹,

Zhan²,

Zhang³

et al. 2005

Planta med

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Five new sesquiterpene lactones, namely vernchinilides A-E (1-5), along with five known compounds, 8 beta-(2-methylacryloyloxy)hirsutinolide 13-O-acetate (6), 8 alpha-(2-methylacryloyloxy)-1beta,4beta-epoxy-1alpha-methoxy-13-O-acetate-10 betaH-germacra-5 E,7(11)-dien-12,6-olide (7), 8 beta-(2-hydroxymethylacryloyloxy)hirsutinolide 13-O-acetate (8), 8 alpha-tigloyloxyhirsutinolide 13-O-acetate ( 9) and vernolide-B (10) were isolated from Vernonia chinensis. The structures of these new compounds were elucidated on the basis of spectral data, especially 2D-NMR techniques. Compounds 2, 5 and 6 exhibited potent cytotoxic activities against P-388 and A-549 tumor cell lines.

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“…49 The triterpenes lupeol (1) and β-amyrin (3) and the flavones velutin (10), apigenin (11) and chrysoeriol (12) were previously isolated from V. nudiflora. 23 Despites the sesquiterpene lactones piptocarphin A (6), B (7) and D (8) already described in other Vernonanthura and Vernonia species, [50][51][52][53] this is the first report of piptocarphins in V. nudiflora. Also, this is the first description of the presence of 2, 4-5 and 13-17 in V. nudiflora aerial parts besides the report of the new hirsutinolide sesquiterpene lactone 9.…”

Section: Resultsmentioning

confidence: 96%

“…41 The 13 , all these signals corroborate the skeleton of a hirsutinolide-type sesquiterpene. 40,42,51 In addition, the 1 H and 13 C NMR spectra showed an olefinic signal at d H 7.06 (q, J 7. (Figure 2).…”

Section: Resultsmentioning

confidence: 98%

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Chemical Constituents, Antiproliferative and Antioxidant Activities of Vernonanthura nudiflora (Less.) H. Rob. Aerial Parts

Ramos

Peixoto

Cabral

et al. 2019

J. Braz. Chem. Soc.

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Sesquiterpene lactones are an important class of secondary metabolites frequently isolated from Vernonanthura genus that present a variety of biological properties, including antiproliferative activity. Due to the limitation of pharmacological studies on Vernonanthura nudiflora, the aim of this work was to investigate their antioxidant potential and antiproliferative activity against human tumor cells, as well as to isolate and identify the chemical constituents present in their aerial parts. The phytochemical investigation resulted in the isolation of the sesquiterpene lactones piptocarphins A, B, D, and a new hirsutinolide derivative, 8α-tigloyloxy-10α-hydroxy-hirsutinolide, besides triterpenes, glycosylated steroids, flavonoids, and one chlorogenic acid derivative. Also, other sesquiterpene lactones were identified by ultra-high performance liquid chromatography-high resolution tandem mass spectrometry (UHPLC-HRMS/MS) from dichloromethane fraction. This fraction showed activity against the tumor cells tested, mainly against leukemia, glioma, ovarian and kidney, with growth inhibitory activity (GI 50) less than 0.80 μg mL-1. Piptocarphins A and B, in mixture, showed strong activity against all human cancer cell lines tested, with GI 50 values ≤ 0.15 μg mL-1. Piptocarphin D was selective for glioma and resistant ovarian cell lines. The new hirsutinolide derivative showed potent activity against breast (GI 50 = 0.96 μg mL-1) and resistant ovarian (GI 50 = 3.60 μg mL-1) cell lines.

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Glaucolides and related sesquiterpene lactones from Vernonia chamaedrys

Cited by 21 publications

References 14 publications

ESI‐QTof‐MS characterization of hirsutinolide and glaucolide sesquiterpene lactones: Fragmentation mechanisms and differentiation based on Na⁺/H⁺ adducts interactions in complex mixture

ESI‐QTof‐MS characterization of hirsutinolide and glaucolide sesquiterpene lactones: Fragmentation mechanisms and differentiation based on Na⁺/H⁺ adducts interactions in complex mixture

Sesquiterpene Lactones with Potent Cytotoxic Activities fromVernonia chinensis

Chemical Constituents, Antiproliferative and Antioxidant Activities of Vernonanthura nudiflora (Less.) H. Rob. Aerial Parts

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Glaucolides and related sesquiterpene lactones from Vernonia chamaedrys

Cited by 21 publications

References 14 publications

ESI‐QTof‐MS characterization of hirsutinolide and glaucolide sesquiterpene lactones: Fragmentation mechanisms and differentiation based on Na+/H+ adducts interactions in complex mixture

ESI‐QTof‐MS characterization of hirsutinolide and glaucolide sesquiterpene lactones: Fragmentation mechanisms and differentiation based on Na+/H+ adducts interactions in complex mixture

Sesquiterpene Lactones with Potent Cytotoxic Activities fromVernonia chinensis

Chemical Constituents, Antiproliferative and Antioxidant Activities of Vernonanthura nudiflora (Less.) H. Rob. Aerial Parts

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ESI‐QTof‐MS characterization of hirsutinolide and glaucolide sesquiterpene lactones: Fragmentation mechanisms and differentiation based on Na⁺/H⁺ adducts interactions in complex mixture

ESI‐QTof‐MS characterization of hirsutinolide and glaucolide sesquiterpene lactones: Fragmentation mechanisms and differentiation based on Na⁺/H⁺ adducts interactions in complex mixture