Mechanism of Chemical Degradation and Determination of Solubility by Kinetic Modeling of the Highly Unstable Sesquiterpene Lactone Nobilin in Different Media

Thormann, Ursula; Mieri, Maria De; Neuburger, Markus; Verjee, Sheela; Altmann, Peter; Hamburger, Matthias; Imanidis, Georgios

doi:10.1002/jps.24100

Cited by 9 publications

(6 citation statements)

References 44 publications

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“…The H-1/H-6 trans-relationships was determined considering the NMR signal of H-1 ( δ H 1.53, td, J = 10.8, 3.1 Hz), which indicated diaxial interactions of this hydrogen with H-6 and H-2β, and an axial-equatorial coupling with H-2α. The configuration at C-10 was resolved take into consideration the resonance of the C-14 methyl at δ C 21.0, which is typical of an axial stereochemistry, because the chemical shifts described for axial and equatorial orientation of this methyl are δ C 21.6 and 28.0, respectively [ 38 ]. This stereochemistry was confirmed in the NOESY spectrum with an axial correlation of H-2β with H-14.…”

Section: Resultsmentioning

confidence: 99%

Sesquiterpene Lactones from Artemisia absinthium. Biotransformation and Rearrangement of the Insect Antifeedant 3α-hydroxypelenolide

Fraga

Díaz

Bailén

et al. 2021

Plants

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Three new compounds, the sesquiterpenes absilactone and hansonlactone and the acetophenone derivative ajenjol, have been isolated from a cultivated variety of Artemisia absinthium. In addition, the major lactone isolated, 3α-hydroxypelenolide, was biotransformed by the fungus Mucor plumbeus affording the corresponding 1β, 10α-epoxide. A cadinane derivative was formed by an acid rearrangement produced in the culture medium, but not by the enzymatic system of the fungus. Furthermore, 3α-hydroxypelenolide showed strong antifeedant effects against Leptinotarsa decemlineata and cytotoxic activity to Sf9 insect cells, while the biotransformed compounds showed antifeedant postingestive effects against Spodoptera littoralis.

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Section: Resultsmentioning

confidence: 99%

Sesquiterpene Lactones from Artemisia absinthium. Biotransformation and Rearrangement of the Insect Antifeedant 3α-hydroxypelenolide

Fraga

Díaz

Bailén

et al. 2021

Plants

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“…Close inspection of the NMR data revealed that 15 was the 3-hydroxy derivative of a cadinane that had been previously obtained by a reaction of nobilin with acids, whereby the transannular cyclization of the 1(10) double bond was facilitated by the alkyl–oxygen cleavage of the lactone ring. The reaction led to the formation of a single bond, C-5/C-10, which transformed the cyclodecadiene into a decaline ring system [ 7 , 8 ].…”

Section: Resultsmentioning

confidence: 99%

“…It is well established that the outcome of the cyclization depends on the spatial rearrangement of the cyclodecadiene ring and, therefore, on the stereochemistry of the diene. We recently reported on the spontaneous rearrangement of nobilin 1 , an E , Z -germacranolide isolated from the flowers of Roman chamomile ( Anthemis nobilis ) in aqueous media under physiological conditions [ 7 ]. We then investigated the rearrangement of 1 in aqueous and organic acidic media and found a transformation into various cadinane derivatives [ 8 ].…”

Section: Introductionmentioning

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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“…Recently, Colantuono et al [38] evaluated the potential bioaccessibility and functionality of polyphenols and cynaropicrin from breads enriched with artichoke stem; the authors showed that 82% of polyphenols and that 74% of cynaropicrin were bioaccessible in duodenal step whilst 88% of caffeic acid was solubilized during the colon step. As reported in literature, some sesquiterpenoids are sensitive to a wide range of chemical and biological modifications; therefore, according to Colantuono et al [38], it is plausible to postulate their degradation by the simulated physiological conditions rather than a not effective extraction by the aqueous digestive fluids [43]. Further ad hoc studies focusing on sesquiterpenoids are needed to clarify the mechanisms underlying sesquiterpene lactones bioaccessibility.…”

Section: In Vitro Bioaccessibility and Bioavailability Of Polyphenolsmentioning

confidence: 97%

Polyphenols and Sesquiterpene Lactones from Artichoke Heads: Modulation of Starch Digestion, Gut Bioaccessibility, and Bioavailability following In Vitro Digestion and Large Intestine Fermentation

2020

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Artichoke is a relevant source of health-promoting compounds such as polyphenols and sesquiterpene lactones. In this study, the bioaccessibility and gut bioavailability of artichoke constituents were evaluated by combining in vitro digestion and large intestine fermentation, metabolomics, and Caco-2 human intestinal cells model. Moreover, the ability of artichoke polyphenols to modulate the in vitro starch digestibility was also explored. An untargeted metabolomic approach based on liquid chromatography quadrupole-time-of-flight (UHPLC/QTOF) mass spectrometry coupled with multivariate statistics was used to comprehensively screen the phytochemical composition of raw, digested, and fermented artichoke. Overall, a large abundance of phenolic acids and sesquiterpene lactones was detected, being 13.77 and 11.99 mg·g−1, respectively. After 20 h of in vitro large intestine fermentation, a decrease in polyphenols and sesquiterpene lactones content was observed. The most abundant compounds characterizing the raw material (i.e., chlorogenic acid and cynaropicrin equivalents) showed an average % bioaccessibility of 1.6%. The highest % bioaccessibility values were recorded for flavonoids such as anthocyanin and flavone equivalents (on average, 13.6%). However, the relatively high bioavailability values recorded for flavonols, phenolic acids, and sesquiterpene lactones (from 71.6% up to 82.4%) demonstrated that these compounds are able to be transported through the Caco-2 monolayer. The phenolic compounds having the highest permeation rates through the Caco-2 model included low molecular weight phenolics such as tyrosol and 4-ethylcatechol; the isoflavonoids 3′-O-methylviolanone, equol 4′-O-glucuronide, and hydroxyisoflavone; together with the methyl and acetyl derivatives of glycosylated anthocyanins. Therefore, although human in vivo confirmatory trials are deemed possible, current findings provide insights into the mechanistic effects underlying artichoke polyphenols and sesquiterpenoids bioavailability following gastrointestinal and large intestine processes.

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Mechanism of Chemical Degradation and Determination of Solubility by Kinetic Modeling of the Highly Unstable Sesquiterpene Lactone Nobilin in Different Media

Cited by 9 publications

References 44 publications

Sesquiterpene Lactones from Artemisia absinthium. Biotransformation and Rearrangement of the Insect Antifeedant 3α-hydroxypelenolide

Sesquiterpene Lactones from Artemisia absinthium. Biotransformation and Rearrangement of the Insect Antifeedant 3α-hydroxypelenolide

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

Polyphenols and Sesquiterpene Lactones from Artichoke Heads: Modulation of Starch Digestion, Gut Bioaccessibility, and Bioavailability following In Vitro Digestion and Large Intestine Fermentation

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