Athenolide A, a New Steroidal Lactone from the Leaves of Athenaea martiana (Solanaceae) Determined by Means of HPLC‐HR‐MS‐SPE‐NMR Analysis

Abstract

Athenaea (Solanaceae) is an endemic genus belonging to the Brazilian Atlantic Rainforest. Recently, botanical investigations suggested the re‐evaluation of the generic status of the genus Athenaea as a synonym of Aureliana. In this study, the first investigation of the Athenaea genus performed on Athenaea martiana by means of HPLC‐HR‐MS‐SPE‐NMR combined with high‐resolution radical scavenging profile led to identification of several phenolic acids as radical scavengers: protocatechuic acid (1), 4‐hydroxybenzoic acid (2), caffeic acid (3), vanillic acid (4), and ferulic acid (6). Additional analysis revealed a new steroidal lactone, named athenolide A (9). Their structures were elucidated by extensive use of NMR spectroscopy as well as HR‐MS. Chemotaxonomic considerations based on these results supported the chemical relationships between the Athenaea and Aureliana genera, in agreement with the recent botanical findings.

A Withanolide-rich Fraction of Athenaea velutina Induces Apoptosis and Cell Cycle Arrest in Melanoma B16F10 Cells

“…The fragmentation pattern of withanolides was established by the successive loss of water molecules and subse- quent cleavage of the lactone group [17]. Similarly to the literature, 3 different structural classes of withanolides have been reported in the Athenaea genus: 5,6-epoxides (3, 5, 6, and 12), 6,7-epoxides (1, 2, and 9), and 5-ene withanolide (4, 7, and 10) [7,9,18]. Considering the metabolite profiling of FAv_5, one can notice an enrichment of withanolides compounds.…”

“…Four major peaks were observed in the chromatographic profile (▶ Fig. 1 a) and a total of 14 possible withanolides (1)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14) were tentatively identified in FAv_5 (▶ Table 2), based on the chemical structure, fragmentation pattern, and by comparison with relevant literature data and the Dictionary of Natural Products (DNP) database. MS/MS spectra obtained for each compound are provided in the Supplementary material (Fig.…”

“…However, further research was needed to confirm this antitumor potential and correlate the respective bioactive compounds. Species of the genus Athenaea have been poorly studied, although their witha-nolide contents with leishmanicidal effects have been reported [7][8][9].…”

NMR-Based Chromatography Readouts: Indispensable Tools to “Translate” Analytical Features into Molecular Structures

“…HPLC-SPE-NMR orientated research is always oriented towards the structural characterization of analytes. Major metabolite classes addressed in recent years were, for example, alkaloids [ 117 , 118 , 119 , 120 , 121 ], diarylheptanoids [ 122 ], flavonoids [ 123 , 124 ], isoflavonoids [ 125 ], chromenes [ 126 ], lignans [ 127 , 128 ], phenanthrenes [ 129 ], terpenoids of different sub-classes [ 130 , 131 , 132 ], steroids [ 133 , 134 ], iridoids [ 135 ], polyphenols [ 136 ], and saponins [ 137 , 138 ].…”

Combination of Pseudo-LC-NMR and HRMS/MS-Based Molecular Networking for the Rapid Identification of Antimicrobial Metabolites From Fusarium petroliphilum

“…One way to solve these problems and to improve both spectral quality and sensitivity was the introduction of solid phase extraction (SPE) in the LC-NMR process, which resulted in the development of the LC-SPE-NMR (Lambert et al, 2007;Gebretsadik et al, 2021). Several recent works have demonstrated the benefits of this approach to working on natural extracts (Silva et al, 2018;Chu et al, 2019;Li et al, 2019). A limitation, however, may be that this approach often requires repeated collection of chromatographic peaks in order to yield sufficient amounts of metabolites from given LC peaks of interest.…”