Aristolochic acids (AAs) are nephrotoxic and carcinogenic nitrophenanthrene carboxylic acids produced naturally by plants from the Aristolochia and Asarum genera, which have been used extensively as ...herbal medicines. In addition to consuming AA-containing herbal medicinal products, there is emerging evidence that humans are also exposed to AA through the environment. In 2022, the World Health Organization (WHO) called for global action to remove AA exposure sources and to implement preventative measures against the development of AA-associated cancers. Herein, we report the development of a simple and efficient iron powder-packed reduction column that allows online post-column conversion of the nonfluorescing AA to its corresponding strongly fluorescing aristolactam (AL), facilitating the sensitive and selective detection of AA in herbal medicinal products, food grain, arable soil, or groundwater samples by high-performance liquid chromatography with fluorescence detection. Moreover, AL, a group of naturally occurring derivatives of AA that have demonstrated toxicity to cultured bacteria, human cells, and rats, is monitored and quantified simultaneously with AA in one single run without sacrificing sensitivity. In comparison with existing analytical methods for AA measurement, the newly developed method is not only inexpensive and less laborious, but it also offers improved sensitivity. We believe this novel method will find wide application in identifying the presence of AA in food, herbal medicines, and environmental samples, thus assisting in the identification and removal of AA exposure sources.
Herein, the results of the first study of non-flavonoid constituents of aboveground surface-wax washings of Primula veris L. (Primulaceae) are presented. Chromatography of the washings yielded a ...minor fraction composed of n-, iso-, and anteiso-series of long-chained syn-1-phenylalkane-1,3-diyl diacetates, 3-oxo-1-phenylalkan-1-yl acetates, 1-phenylalkane-1,3-diones, 1-hydroxy-1-phenylalkan-3-ones, sec-alcohols (2- to 10-alkanols), and n-, iso-, anteiso-, 2-methylalkanoic and 3-methylalkanoic acids; 118 of these constituents represent up to now unreported natural compounds. The structural/stereochemical elucidation was accomplished by the synthesis of authentic standards, derivatization reactions, the use of gas chromatographic retention data and detailed 1D and 2D-NMR analyses of the obtained complex chromatographic fraction. Primula veris produces unusually high amounts of branched long-chained metabolites (>60%) except for the fatty acids where the percentage of branched isomers is comparable to the ones with n-chains. Noteworthy is the fact that long-chained α- and β-methyl substituted fatty acids were detected herein for the first time in the kingdom Plantae.
Display omitted
•Non-flavonoid constituents of P. veris surface waxes were analyzed in detail.•118 unreported natural compounds were identified in a wax chromatographic fraction.•Unusually, branched-chain metabolites dominated in the detected compound series.•α- and β-methyl substituted fatty acids were detected for the first time in Plants.•Identification required synthesis, derivatization, GC-MS and NMR analyses.
Immortelle (Helichrysum italicum, Asteraceae) essential oil has been widely used in alternative medicine to accelerate wound healing, as well as in cosmetic products to stimulate skin regeneration ...and to reduce the appearance of wrinkles. It is also considered a natural and safe culinary spice that could also be applied in the food industry as a preservative in the future. The therapeutic efficacy of this oil changes with the natural variability of the composition. Herein we tested and mutually compared the antimicrobial and anti-inflammatory activities of four commercial immortelle oils differing in the relative amounts of marker compounds, i.e. neryl esters, α-pinene, γ- and ar-curcumenes, and β-diketones. The anti-inflammatory effect of selected chromatographic fractions, enriched in the aforementioned constituents, was evaluated by studying toxicity toward rat peritoneal macrophages, their nitric oxide production, myeloperoxidase, and arginase activities. Subsequently, the compositional and activity data were subjected to a multivariate statistical treatment to reveal the possible correlation(s) between the percentage of essential-oil constituents and the observed activities. The obtained results imply that immortelle oil efficiency as an antimicrobial and/or anti-inflammatory agent is most plausibly a result of a synergistic action between its constituents, and/or, rather unexpectedly, the presence of some minor constituents.
•Helichrysum italicum essential oil (EO) is used to promote wound healing.•Variations in the EO composition apparently affect its toxicity/bioactivity.•The tested EOs displayed strong antimicrobial and anti-inflammatory effects.•Unexpected links between the constituent amount and the toxicity were established.•Minor constituent presence and synergistic action define the modus operandi.
Herein n‐, iso‐ and anteiso‐series of very‐long‐chained (VLC) alkanes (C21–C35), fatty acid benzyl esters (FABEs; C20–C32), and 2‐alkanones (C23–C35) were identified in the wax of Primula veris L. ...and P. acaulis (L.) L. (Primulaceae). For the very first time in a sample of natural origin, the presence of iso‐ and anteiso‐VLC FABEs and 2‐alkanones was unequivocally confirmed by synthetic work, derivatization, and NMR. It should be noted that the studied species produced unusually high amounts of branched wax constituents (e. g., >50 % of 2‐alkanones were branched isomers). The domination of iso‐isomers, probably biosynthesized from leucine‐derived starters, is a unique feature in the Plant Kingdom. The plant organ distribution of these VLC compounds in P. acaulis samples (different habitats and phenological phases) pointed to their possible ecological value. This was supported by a eutectic behavior of binary blends of FABEs and alkanes, as well as by high UV‐C absorption by FABEs.
Helichrysum italicum (immortelle) is a dwarf aromatic shrub native to the Mediterranean region. The typical subspecies (italicum) produces an essential oil rich in neryl acetate and characteristic ...β-diketones, italidiones, highly valued in the perfume industry. As esters are an important group of aroma-active volatiles, herein the composition of the ester fraction of this immortelle chemotype essential oil was studied in detail. Chromatographic separation of Corsican immortelle essential oil enabled the discovery of numerous potentially olfactory-interesting esters of nerol and/or angelic acid, undetectable by direct GC-MS analyses of the unfractioned oil. Four esters of nerol and medium-chain branched fatty acids represent new natural products, while several other esters have a rather restricted occurrence in the Plant Kingdom.
Keywords Primula veris L.; Primulaceae; Branched long-chain wax constituents; syn-1-Phenylalkane-1,3-diyl diacetates; 3-Oxo-1-phenylalkan-1-yl acetates; 1-Phenylalkane-1,3-diones; sec-Alcohols; ...2-Methylalkanoic and 3-methylalkanoic acids Highlights * Non-flavonoid constituents of P. veris surface waxes were analyzed in detail. * 118 unreported natural compounds were identified in a wax chromatographic fraction. * Unusually, branched-chain metabolites dominated in the detected compound series. * alpha- and beta-methyl substituted fatty acids were detected for the first time in Plants. * Identification required synthesis, derivatization, GC-MS and NMR analyses. Herein, the results of the first study of non-flavonoid constituents of aboveground surface-wax washings of Primula veris L. (Primulaceae) are presented. Chromatography of the washings yielded a minor fraction composed of n-, iso-, and anteiso-series of long-chained syn-1-phenylalkane-1,3-diyl diacetates, 3-oxo-1-phenylalkan-1-yl acetates, 1-phenylalkane-1,3-diones, 1-hydroxy-1-phenylalkan-3-ones, sec-alcohols (2- to 10-alkanols), and n-, iso-, anteiso-, 2-methylalkanoic and 3-methylalkanoic acids; 118 of these constituents represent up to now unreported natural compounds. The structural/stereochemical elucidation was accomplished by the synthesis of authentic standards, derivatization reactions, the use of gas chromatographic retention data and detailed 1D and 2D-NMR analyses of the obtained complex chromatographic fraction. Primula veris produces unusually high amounts of branched long-chained metabolites (>60%) except for the fatty acids where the percentage of branched isomers is comparable to the ones with n-chains. Noteworthy is the fact that long-chained alpha- and beta-methyl substituted fatty acids were detected herein for the first time in the kingdom Plantae. Author Affiliation: Department of Chemistry, Faculty of Sciences and Mathematics, University of Nis, Visegradska 33, 18000, Nis, Serbia * Corresponding author. Article History: Received 28 August 2020; Revised 27 February 2021; Accepted 5 March 2021 Byline: Niko S. Radulovic nikoradulovic@yahoo.com (*), Milena Z. Zivkovic Stosic
