Simultaneous LC-MS quantification of anthocyanins and non-anthocyanin phenolics from blueberries with widely divergent profiles and biological activities

Abstract

A sensitive and straightforward LC-IT-TOF-MS method was validated for the profiling and simultaneous quantification of anthocyanins, flavan-3-ols, flavonols, phenolic acids, and resveratrol in blueberry genotypes with fruit color ranging from deep purple (Vaccinium angustifolium) to various shades of pink (crosses of V. corymbosum, V. darrowii, and V. ashei). Standard calibration curves were linear for all analytes with correlation coefficients >0.99. The relative standard deviation for intra-and inter-day precision was lower than 10%. The method allowed an easy and selective identification and quantification of phenolics in blueberries with divergent profiles. The in vitro antioxidant assay results were strongly correlated with total phenolics and total anthocyanin content. Lowbush blueberry extracts (50 μg/mL) reduced ROS and NO production, and inhibited the transcription of the proinflammatory cytokines IL-6β, COX2, iNOS, and IL-6 in the in vitro assays at much lower concentrations than pink fruited berries (250 μg/mL).

Development of a genetic framework to improve the efficiency of bioactive delivery from blueberry

“…To quantify phenolics including ANC and non-ANC, commercially cultivated blueberries (unknown variety) were purchased at a local store in Kannapolis, NC (Supplementary Table S1). The composition was consistent with previous reports 18,20,21,48,49 . Among phenolics, ANC accounted for 283 mg/100 g FW within the form of simple glycosides (-3-O-galactoside (Galc), -3-O-glucoside (Gluc) and -3-O-arabinoside (Arab)) in relative abundance of malvidin (Mal) > petunidin (Pet) > cyanidin (Cyan) > peonidin (Peo) > delphinidin (Del).…”

Diversity in Metabolites and Fruit Quality Traits in Blueberry Enables Ploidy and Species Differentiation and Establishes a Strategy for Future Genetic Studies

“…Extensive variation for concentrations and fruit quality traits was identified in this study, especially within the tetraploid accessions. Bioactive metabolite analysis identified 20 anthocyanins, 6 flavonols, 4 flavanols and 4 phenolic acids, in agreement with type and number of flavonoids and polyphenols observed in previous studies (Grace et al, 2019;Wang et al, 2019). We detected a pronounced accession, year and accession by year interaction effects on the metabolite concentrations.…”

“…Important health-promoting bioactive metabolites, including flavonoids (anthocyanins, flavanols, and flavonols) and nonflavonoids such as phenolic acids, are found abundantly in blueberry (Kalt et al, 2001;Rodriguez-Mateos et al, 2012;Yousef et al, 2013Yousef et al, , 2014Gündüz et al, 2015;Scalzo et al, 2015;Li et al, 2017;Timmers et al, 2017;Grace et al, 2019;Wang et al, 2019). In blueberry, anthocyanins are the most abundant flavonoids, and are derivative of anthocyanidins (aglycones) by the addition of sugar moieties.…”

“…The anthocyanidins can be conjugated with sugar moieties like arabinoside, glucosides, and galactoside via the C3 hydroxyl group in ring C, and form structurally different anthocyanins. The conjugation of anthocyanidins with sugar moieties can be further modified through acylation (Norberto et al, 2013;Yousef et al, 2014;Li et al, 2017;Grace et al, 2019;Wang et al, 2019). Various patterns of conjugated sugar moieties, with or without acylation, can affect the chemical properties of anthocyanins, such as stability and bioavailability.…”

“…Caffeic, ferulic, and chlorogenic acids are commonly reported phenolic acids. Of these, chlorogenic acid is the most abundant phenolic acid in blueberry (Grace et al, 2019;Wang et al, 2019). Similarly, flavanols (epi-catechin, catechin, proanthocyanidin B 1 , and proanthocyanidin B 2 ) and flavonols (kaempferol, quercetin, and myricetin) are also commonly reported flavonoids in blueberry (Grace et al, 2019;Wang et al, 2019).…”