Antiprotozoal Activity-Based Profiling of a Dichloromethane Extract from <i>Anthemis nobilis</i> Flowers

Mieri, Maria De; Monteleone, Giannicola; Ismajili, Isidor; Kaiser, Marcel; Hamburger, Matthias

doi:10.1021/acs.jnatprod.6b00980

Cited by 28 publications

(14 citation statements)

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“…Previously identified in Vernonanthura species, peaks XIII and XIV were respectively characterized as 8‐tigloyloxy‐glaucolide A and glaucolide G. Moreover, 8‐tigloyloxy‐glaucolide A was already characterized in V. tweedieana species . The putative elution order was based on the literature, wherein 8‐tigloyloxy‐glaucolide A has a lower t R relative to the glaucolide G, which suggested a higher t R for angelate than tiglate isomers in UPLC separation.…”

Section: Resultsmentioning

confidence: 85%

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: 85%

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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“…For the minor compound 7 of the mixture, a strong NOESY cross peak between H-9 and H 3 -14 (δ H = 5.30 and 1.80, respectively) supported the cis configuration of the double bond at C-9/C-10 ( Figure S28 ). Interestingly, the C-1 epimer of compound 7 has recently been isolated from Anthemis nobilis [ 17 ].…”

Section: Resultsmentioning

confidence: 99%

Acid-Induced Rearrangement of Epoxygermacranolides: Synthesis of Furanoheliangolides and Cadinanes from Nobilin

et al. 2017

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The acid-induced rearrangement of three epoxyderivatives of nobilin 1, the most abundant sesquiterpene lactone in Anthemis nobilis flowers, was investigated. From the 1,10-epoxyderivative 2, furanoheliangolide 5 was obtained, while the 4,5-epoxy group of 3 did not react. Conversely, when the 3-hydroxy function of nobilin was acetylated (12), the 4,5-epoxy derivative did cyclize into cadinanes (15 and 16) under Lewis acid catalysis. The reactivity of the 4,5- and 1,10-epoxy derivatives of nobilin (2 and 3) was compared with that of parthenolide, and rationalized on the basis of quantum chemical calculations. All isolated reaction products were fully characterized by spectroscopic and computational methods, and their in vitro anti-protozoal activity was evaluated. The paper could provide new insights into the biosynthesis of this class of natural products.

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“…[24], Compounds 85 and 86 from Lepidaploa rufogrisea [24], Compound 87 from Tarchonanthus camphoratus [5], Compounds 88 – 107 from Schkuhria pinnata [5], Compounds 108 – 113 from Vernonia lasiopus [7], and 114 – 118 from V. cinerascens [6]. The activity data of 119 – 130 , all isolated from Anthemis nobilis , was extracted from literature having been determined under the same conditions at the Swiss Tropical and Public Health Institute (STPH) laboratory [25] (see Figure 1 for all structures). Three-dimensional (3D) molecular models of the 130 STLs were generated with Molecular Operating Environment (MOE; version 2016.8; Chemical Computing Group, Montreal, QC., Canada).…”

Section: Methodsmentioning

confidence: 99%

Complementary Quantitative Structure–Activity Relationship Models for the Antitrypanosomal Activity of Sesquiterpene Lactones

Kimani¹,

Matasyoh

Kaiser

et al. 2018

IJMS

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Three complementary quantitative structure–activity relationship (QSAR) methodologies, namely, regression modeling based on (i) “classical” molecular descriptors, (ii) 3D pharmacophore features, and (iii) 2D molecular holograms (HQSAR) were employed on the antitrypanosomal activity of sesquiterpene lactones (STLs) toward Trypanosoma brucei rhodesiense (Tbr), the causative agent of the East African form of human African trypanosomiasis. In this study, an extension of a previous QSAR study on 69 STLs, models for a much larger and more diverse set of such natural products, now comprising 130 STLs of various structural subclasses, were established. The extended data set comprises a variety of STLs isolated and tested for antitrypanosomal activity within our group and is furthermore enhanced by 12 compounds obtained from literature, which have been tested in the same laboratory under identical conditions. Detailed QSAR analyses yielded models with comparable and good internal and external predictive ability. For a set of compounds as chemically diverse as the one under study, the models exhibited good coefficients of determination (R2) ranging from 0.71 to 0.85, as well as internal (leave-one-out Q2 values ranging from 0.62 to 0.72) and external validation coefficients (P2 values ranging from 0.54 to 0.73). The contributions of the various tested descriptors to the generated models are in good agreement with the results of previous QSAR studies and corroborate the fact that the antitrypanosomal activity of STLs is very much dependent on the presence and relative position of reactive enone groups within the molecular structure but is influenced by their hydrophilic/hydrophobic properties and molecular shape.

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Antiprotozoal Activity-Based Profiling of a Dichloromethane Extract from Anthemis nobilis Flowers

Cited by 28 publications

References 35 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

Acid-Induced Rearrangement of Epoxygermacranolides: Synthesis of Furanoheliangolides and Cadinanes from Nobilin

Complementary Quantitative Structure–Activity Relationship Models for the Antitrypanosomal Activity of Sesquiterpene Lactones

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Antiprotozoal Activity-Based Profiling of a Dichloromethane Extract from Anthemis nobilis Flowers

Cited by 28 publications

References 35 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

Acid-Induced Rearrangement of Epoxygermacranolides: Synthesis of Furanoheliangolides and Cadinanes from Nobilin

Complementary Quantitative Structure–Activity Relationship Models for the Antitrypanosomal Activity of Sesquiterpene Lactones

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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