Metabolite Profiling of Jaboticaba (Myrciaria cauliflora) and Other Dark-Colored Fruit Juices

Many dark-colored fruit juices, rich in anthocyanins, are thought to be important for human health. Joboticaba (Myrciaria cauliflora) fruits, native to Brazil, have phenolics including anthocyanins and are processed into juice and other products. The phenolic constituents in the fruits of jaboticaba were studied by high-performance liquid chromatography coupled with electrospray ionization time-of-flight mass spectrometry. Twenty-two compounds were identified or tentatively determined by detailed analysis of their mass spectral fragmentation patterns; 11 compounds including 7 gallotannins, 2 ellagic acid derivatives, syringin, and its glucoside were detected for the first time in the fruit. The compositional differences among the fruit extracts and their commercial products were also compared by principal component analysis; two anthocyanins, delphinidin 3-<i>O</i>-glucoside and cyanidin-3-<i>O</i>-glucoside, as well as two depsides, jaboticabin and 2-<i>O</i>-(3,4-dihydroxybenzoyl)-2,4,6-trihydroxyphenylacetic acid, present in the fruit extracts were not detected unexpectedly in commercial jaboticaba juice or jam. Therefore, the stability of anthocyanins in jaboticaba fresh fruits and products has been compared directly with that of other dark-colored fruit products made from blueberry and Concord grape, and the same trend of decreasing amounts of anthocyanins was observed in all tested products. The antioxidant activities (DPPH^• and ABTS^•+) of jaboticaba fresh fruit extract and commercial samples were also compared. Principal component analysis proved to be a useful way to discern changes between fresh and processed fruits. Jaboticaba is a promising fruit with antioxidant capacity similar to those of other so-called superfruits; however, during processing the levels of some of anthocyanins and other polyphenols decrease significantly, and therefore the capacity of these products to affect human health may vary significantly from that of the fresh fruit

Antioxidants from <i>Gerbera piloselloides</i>: an ethnomedicinal plant from southwestern China

<div><p><i>Gerbera piloselloides</i> is a very important ethnobotanical and ethnomedicinal plant used by indigenous peoples in southwestern China. Ten compounds were obtained using activity-guided isolation, including a parasorbosid derivative, two caffeic acid derivatives, two coumarins and five flavonoids, and identified from the whole plant of <i>G. piloselloides</i>. This is the first report of compound <b>5</b> as natural product. Six compounds were reported in the <i>Gerbera</i> genus for the first time. The antioxidant activity of all the compounds was evaluated by using ABTS assay, and the chemotaxonomic implication of this study was also discussed.</p></div

Bioactive and Marker Compounds from Two Edible Dark-Colored <i>Myrciaria</i> Fruits and the Synthesis of Jaboticabin

Jaboticaba (<i>Myrciaria cauliflora</i>) and false jaboticaba (<i>Myrciaria vexator</i>) fruits are two pleasant-tasting, dark-colored fruits, native to Brazil. They are rich sources of phenolic compounds, including anthocyanins, flavonoids, phenolic acids, and tannins, as well as less well known polyphenols such as depsides. These two fruits are very similar in morphology, but their taste profiles differ markedly. This study was focused on identifying the marker compounds between them using HPLC-PDA and LC-TOF-MS, combined with principal component analysis. As a result, cyanidin-3-<i>O</i>-glucoside was found as the major anthocyanin in <i>Myrciaria</i> fruits. Delphinidin-3-<i>O</i>-glucoside was found to be the marker compound for jaboticaba, while cyanidin-3-<i>O</i>-galactoside and cyanidin-3-<i>O</i>-arabinose were two marker compounds distinguishing false jaboticaba. In addition, two ellagitannins, iso-oenothein C and oenothein C, were isolated and identified from both of these fruits for the first time. Jaboticabin, a minor bioactive depside, occurred in both fruits and, because of its potential to treat chronic obstructive pulmonary disease, was successfully synthesized in the laboratory

Antioxidant and Metabolite Profiling of North American and Neotropical Blueberries Using LC-TOF-MS and Multivariate Analyses

There are many neotropical blueberries, and recent studies have shown that some have even stronger antioxidant activity than the well-known edible North American blueberries. Antioxidant marker compounds were predicted by applying multivariate statistics to data from LC-TOF-MS analysis and antioxidant assays of 3 North American blueberry species (Vaccinium corymbosum, Vaccinium angustifolium, and a defined mixture of Vaccinium virgatum with <i>V. corymbosum</i>) and 12 neotropical blueberry species (Anthopterus wardii, Cavendishia grandifolia, Cavendishia isernii, Ceratostema silvicola, Disterigma rimbachii, Macleania coccoloboides, Macleania cordifolia, Macleania rupestris, Satyria boliviana, Sphyrospermum buxifolium, Sphyrospermum cordifolium, and Sphyrospermum ellipticum). Fourteen antioxidant markers were detected, and 12 of these, including 7 anthocyanins, 3 flavonols, 1 hydroxycinnamic acid, and 1 iridoid glycoside, were identified. This application of multivariate analysis to bioactivity and mass data can be used for identification of pharmacologically active natural products and may help to determine which neotropical blueberry species will be prioritized for agricultural development. Also, the compositional differences between North American and neotropical blueberries were determined by chemometric analysis, and 44 marker compounds including 16 anthocyanins, 15 flavonoids, 7 hydroxycinnamic acid derivatives, 5 triterpene glycosides, and 1 iridoid glycoside were identified

Antioxidant and Metabolite Profiling of North American and Neotropical Blueberries Using LC-TOF-MS and Multivariate Analyses

There are many neotropical blueberries, and recent studies have shown that some have even stronger antioxidant activity than the well-known edible North American blueberries. Antioxidant marker compounds were predicted by applying multivariate statistics to data from LC-TOF-MS analysis and antioxidant assays of 3 North American blueberry species (Vaccinium corymbosum, Vaccinium angustifolium, and a defined mixture of Vaccinium virgatum with <i>V. corymbosum</i>) and 12 neotropical blueberry species (Anthopterus wardii, Cavendishia grandifolia, Cavendishia isernii, Ceratostema silvicola, Disterigma rimbachii, Macleania coccoloboides, Macleania cordifolia, Macleania rupestris, Satyria boliviana, Sphyrospermum buxifolium, Sphyrospermum cordifolium, and Sphyrospermum ellipticum). Fourteen antioxidant markers were detected, and 12 of these, including 7 anthocyanins, 3 flavonols, 1 hydroxycinnamic acid, and 1 iridoid glycoside, were identified. This application of multivariate analysis to bioactivity and mass data can be used for identification of pharmacologically active natural products and may help to determine which neotropical blueberry species will be prioritized for agricultural development. Also, the compositional differences between North American and neotropical blueberries were determined by chemometric analysis, and 44 marker compounds including 16 anthocyanins, 15 flavonoids, 7 hydroxycinnamic acid derivatives, 5 triterpene glycosides, and 1 iridoid glycoside were identified

Antioxidant and Metabolite Profiling of North American and Neotropical Blueberries Using LC-TOF-MS and Multivariate Analyses

There are many neotropical blueberries, and recent studies have shown that some have even stronger antioxidant activity than the well-known edible North American blueberries. Antioxidant marker compounds were predicted by applying multivariate statistics to data from LC-TOF-MS analysis and antioxidant assays of 3 North American blueberry species (Vaccinium corymbosum, Vaccinium angustifolium, and a defined mixture of Vaccinium virgatum with <i>V. corymbosum</i>) and 12 neotropical blueberry species (Anthopterus wardii, Cavendishia grandifolia, Cavendishia isernii, Ceratostema silvicola, Disterigma rimbachii, Macleania coccoloboides, Macleania cordifolia, Macleania rupestris, Satyria boliviana, Sphyrospermum buxifolium, Sphyrospermum cordifolium, and Sphyrospermum ellipticum). Fourteen antioxidant markers were detected, and 12 of these, including 7 anthocyanins, 3 flavonols, 1 hydroxycinnamic acid, and 1 iridoid glycoside, were identified. This application of multivariate analysis to bioactivity and mass data can be used for identification of pharmacologically active natural products and may help to determine which neotropical blueberry species will be prioritized for agricultural development. Also, the compositional differences between North American and neotropical blueberries were determined by chemometric analysis, and 44 marker compounds including 16 anthocyanins, 15 flavonoids, 7 hydroxycinnamic acid derivatives, 5 triterpene glycosides, and 1 iridoid glycoside were identified

Using Ultra-Performance Liquid Chromatography Quadrupole Time of Flight Mass Spectrometry-Based Chemometrics for the Identification of Anti-angiogenic Biflavonoids from Edible Garcinia Species

Garcinia xanthochymus fruits are edible and also used in traditional medicine. Our previous work showed that the isolated natural products from G. xanthochymus fruits have displayed antioxidant activity and cytotoxicity in the colon cancer cells. In this study, we developed a strategy to correlate a zebrafish angiogenesis assay with ultra-performance liquid chromatography quadrupole time of flight mass spectrometry-based chemometric analysis to identify potential anti-angiogenic activity compounds from G. xanthochymus fruits. Primary bioactivity results showed that the methanolic extracts from aril and pericarp but not from seed have significant inhibitory effects on the growth of subintestinal vessels (SIVs) in zebrafish embryos. A total of 13 markers, including benzophenones and biflavonoids, were predicted by untargeted principal component analysis and orthogonal partial least squares discriminate analysis, which were tentatively identified as priority markers for the bioactivity related in aril and pericarp. Amentoflavone, a biflavonoid, has been found to significantly inhibit the growth of SIVs at 10 and 20 μM and downregulate the expressions of <i>Angpt2</i> and <i>Tie2</i> genes of zebrafish embryos. Furthermore, seven biflavonoids, volkensiflavone, fukugetin, fukugeside, GB 1a, GB 1a glucoside, GB 2a, and GB 2a glucoside, isolated from Garcinia species were evaluated for their structure–activity relationship using the zebrafish model. Only fukugetin, which was previously shown to be anticancer, was active in inhibiting the SIV growth. In this report, both amentoflavone and fukugetin, for the first time, displayed anti-angiogenic effects on zebrafish, thus demonstrating an effective and rapid strategy to identify natural products for anti-angiogenesis activity

UPLC-QTOFMS^E‑Guided Dereplication of the Endangered Chinese Species <i>Garcinia paucinervis</i> to Identify Additional Benzophenone Derivatives

A number of <i>Garcinia</i> species accumulate benzophenone derivatives that may be useful for the treatment of breast cancer. The dereplication of new benzophenone derivatives from <i>Garcinia</i> species is challenging due to the occurrence of multiple isomers and the known compounds found in their extracts. In the current study, a strategy is described using the UPLC-QTOFMS^E technique to identify tentatively the known and uncharacterized benzophenones of interest based upon the characteristic fragmentation ions. Several UPLC-QTOFMS peaks (<i>a</i>–<i>ee</i>) appeared to contain benzophenone derivatives, and 12 of these peaks contained compounds with MS ionization profiles not consistent with previously identified compounds from the seeds of <i>Garcinia paucinervis</i>, an endangered Chinese species. The targeted isolation of unidentified compounds of interest afforded five new benzophenones, paucinones E–I (<b>1</b>–<b>5</b>), which were determined by MS and NMR analysis and ECD spectroscopy. These compounds were evaluated for cytotoxicity against three breast cancer cell lines inclusive of MDA-MB-231, SKBR3, and MCF-7. These results indicate that the UPLC-QTOFMS^E-guided isolation procedure is an efficient strategy for isolating new benzophenones from <i>Garcinia</i> species

Cytotoxic oplopane sesquiterpenoids from <i>Arnoglossum atriplicifolium</i>

<p>Pale Indian plantain (<i>Arnoglossum atriplicifolium</i> (L.) H. Rob.) is a plant with traditional medicinal usage among the Cherokee Native American tribe for treating cancer. Two oplopane sesquiterpenoids were isolated from an extract of <i>A. atriplicifolium</i> from Western North Carolina. The compounds were isolated by bioassay-guided fractionation using an MCF-7 breast tumour cell line assay. The known compound (1<i>S</i>,6<i>R</i>,7<i>R</i>,8<i>R</i>)-1-acetoxy-6,7-diangeloxy-8,10-epoxy-2-oxo-oplopa-3,14Z,11,12-dien-13-al (<b>1</b>) had an EC₅₀ value of 9.0 μM against MCF-7 cells, while the new compound (1<i>S</i>,3<i>R</i>,6<i>R</i>,7<i>R</i>,8<i>R</i>,11<i>S</i>)-1-acetoxy-6,7-diangeloxy-8,10,11,13-bisepoxyoplopan-2-one (<b>2</b>) had an EC₅₀ value of 96 μM. The compounds were characterised by 1D and 2D NMR spectroscopy and by comparison with literature values in the case for <b>1</b>. Based on NOESY analysis, a correction of the relative configuration for <b>1</b> is presented. The presence of these compounds may help to explain the folk remedy usage of this plant as an anticancer agent.</p

Metabolomics and Transcriptomics Reveal that Diarylheptanoids Vary in Amomum tsao-ko Fruit Development

Amomum tsao-ko is an important spice and medicinal plant that has received extensive attention in recent years for its high content of bioactive constituents with the potential for food additives and drug development. Diarylheptanoids are major and characteristic compounds in A. tsao-ko; however, the biochemical and molecular foundation of diarylheptanoids in fruit is unknown. We performed comparative metabolomics and transcriptomics studies in the ripening stages of A. tsao-ko fruit. The chemical constituents of fruit vary in different harvest periods, and the diarylheptanoids have a trend to decrease or increase with fruit development. GO enrichment analysis revealed that plant hormone signaling pathways including the ethylene-activated signaling pathway, salicylic acid, jasmonic acid, abscisic acid, and response to hydrogen peroxide were associated with fruit ripening. The biosynthetic pathways including phenylpropanoid, flavonoids, and diarylheptanoids biosynthesis were displayed in high enrichment levels in ripening fruit. The molecular networking and phytochemistry investigation of A. tsao-ko fruit has isolated and identified 10 diarylheptanoids including three new compounds. The candidate genes related to diarylheptanoids were obtained by coexpression network analysis and phylogenetic analysis. Two key genes have been verified to biosynthesize linear diarylheptanoids. This integrative approach provides gene regulation and networking associated with the biosynthesis of characteristic diarylheptanoids, which can be used to improve the quality of A. tsao-ko as food and medicine