UPLC-TOF-MS Characterization and Identification of Bioactive Iridoids inCornus masFruit

Abstract

Cornus mas L. is indigenous to Europe and parts of Asia. Although Cornus is widely considered to be an iridoid rich genera, only two iridoids have been previously found in this plant. The lack of information on taxonomically and biologically active iridoids prompted us to develop and optimize an analytical method for characterization of additional phytochemicals in C. mas fruit. An ultra performance liquid chromatography (UPLC) coupled with photodiode array spectrophotometry (PDA) and electrospray time-of-flight mass spectrometry (ESI-TOF-MS) was employed and mass parameters were optimized. Identification was made by elucidating the mass spectral data and further confirmed by comparing retention times and UV spectra of target peaks with those of reference compounds. Primary DNA damage and antigenotoxicity tests in E. coli PQ37 were used to screen the iridoids for biological activity. As a result, ten phytochemicals were identified, including iridoids loganic acid, loganin, sweroside, and cornuside. Nine of these were reported for the first time from C. mas fruit. The iridoids did not induce SOS repair of DNA, indicating a lack of genotoxic activity in E. coli PQ37. However, loganin, sweroside, and cornuside did reduce the amount of DNA damage caused by 4-nitroquinoline 1-oxide, suggesting potential antigenotoxic activity.

Cornus mas and Cornus Officinalis—Analogies and Differences of Two Medicinal Plants Traditionally Used

“…Secoiridoids are believed to be even more advanced due to the more complicated biostynthetic steps (Xiang et al, 1996). Thus, the most closely related in the iridoids transformation pathway compounds, such as loganin ( 1 ), loganic acid ( 3 ), cornin ( 4 ), sweroside ( 5 ), and representative of secoiridoids, cornuside ( 6 ), have been detected both in fruits of C. mas and C. officinalis (Deng et al, 2013; Ma et al, 2014; Perova et al, 2014; Sochor et al, 2014; Kucharska et al, 2015; Jiang et al, 2016). However, it should be noted that in the 26 cultivars of C. mas it was shown that the most abundant iridoid was loganic acid ( 3 ) (81.5–461.1 mg/100 g fw) constituting 88–96% of total iridoids (86.9–493.7 mg/100 g fw).…”

“…Cornuside ( 6 ) has already followed loganic acid ( 3 ) but its content was much lower than loganic acid ( 3 ) and maximally reached 36.2 mg/100 g fw (West et al, 2012a; Kucharska et al, 2015). Only two reports describe the identification of loganin ( 1 ) and sweroside ( 5 ) in fruit of C. mas (Deng et al, 2013; Perova et al, 2014). Nevertheless, the reason of limited data on identification of loganin and sweroside in fruits of cornelian cherry is due to their low concentration compared to loganic acid.…”

New flavonoids from the fruits of Cornus mas, Cornaceae

“…Previous studies on chemical constituents of the fruits of C. mas 31 reported the isolation of anthocyanins (Du and Francis, 1973a,b;32 Seeram et al, 2002;Tural and Koca, 2008), flavonoids (Pawlowska 33 et al, 2010), iridoids (Deng et al, 2013) and carboxylic acids 34 (Krivoruchko, 2014). Our preliminary study on the C. mas fruit 35 extract using various cancer cells such as lung, prostate, cervical 36 and hepatic cancer cells showed significant cytotoxicity and 37 antibacterial study against pathogenic bacteria, Staphylococcus 38 aureus and Pseudomonas aeruginosa showed good antibacterial 39 activity.…”

Metabolite fingerprinting, pathway analyses, and bioactivity correlations for plant species belonging to the Cornaceae, Fabaceae, and Rosaceae families

“…In the case of the primary metabolites, shikimic acid (2), gallic acid (3), arabinose (16), fructose (21), glucose (22), and myo-inositol (25) were relatively higher in Cornaceae than in Fabaceae and Rosaceae. The fruits of C. mas have been reported as containing significant proportions of organic acids (4.6-7.4 %) and gallic acid was identified (Deng et al 2013). Gallic acid is a known precursor of hydrolysable tannin, which is synthesized from an intermediate precursor named dehydroshikimic acid (Ossipov et al 2003).…”