Analytical Methods Anthocyanins and antioxidant capacities of six Chilean berries by HPLC–HR-ESI-ToF-MS Javier E. Ramirez a , Ricardo Zambrano a , Beatriz Sepúlveda b , Edward J. Kennelly c , Mario J. Simirgiotis a,⇑ a Laboratorio de Productos Naturales, Departamento de Química, Facultad de Ciencias Básicas, Universidad de Antofagasta, Av. Coloso S-N, Antofagasta, Chile b Departamento de Ciencias Químicas, Universidad Andrés Bello, Campus Viña del Mar, Los Fresnos N 52, Viña del Mar 2520000, Chile c Department of Biological Sciences, Lehman College and The Graduate Center, The City University of New York, 250 Bedford Park Boulevard West, Bronx, NY 10468, United States article info Article history: Received 13 November 2013 Received in revised form 27 February 2014 Accepted 11 December 2014 Available online 18 December 2014 Keywords: Chilean berries Anthocyanins Phenolics Antioxidant capacity HPLC–MS healthy edible fruits abstract The HPLC profiles of six fruits endemic of the VIII region of Chile were investigated using high resolution mass analysis (HR-ToF-ESI-MS). The anthocyanin fingerprints generated for the fruits were compared and the antioxidant capacities measured by the scavenging of the DPPH radical, the ferric reducing antioxidant power (FRAP), the superoxide anion scavenging activity assay (SA), and correlated with the inhibition of lipid peroxidation in human erythrocytes (LP) and total content of phenolics, flavonoids and anthocyanins measured by spectroscopic methods. Several anthocyanins were identified, including 3-O-glycosides derivatives of delphinidin, cyanidin, petunidin, peonidin and malvidin. Three phenolic acids (feruloyl-quinic acid, chlorogenic acid, and neochlorogenic acid) and five flavonols (hyperoside, isoquercitrin, quercetin, rutin, myricetin and isorhamnetin) were also identified. Calafate fruits showed the highest antioxidant activity. However, the highest LP activity was found for Chilean blueberries (>95%) followed by calafate fruits (91.27%) and luma (83.4%). Ó 2014 Elsevier Ltd. All rights reserved. 1. Introduction Several epidemiological studies have showed the association between the consumption o foods with high content of phenolics mainly flavonoids and anthocyanins and the prevention of some diseases such as heart attack, cancer and other degenerative disorders (Manach, Scalbert, Morand, Remesy, & Jimenez, 2004; Zamora-Ros et al., 2013). Fruits and vegetables are considered pro- tective for human health due to their content of beneficial com- pounds particularly against various oxidative-stress related diseases (Pennington & Fisher, 2010). Anthocyanins are a group of water soluble polyphenolic pigments widely found in berry fruits which can act as free radical scavengers mitigating oxidative stress (Pojer, Mattivi, Johnson, & Stockley, 2013). The term berry fruit generally refers to small fruits without big seeds that can be eaten whole. Berry fruits are often the richest source of antioxidant phenolics among fruits and vegetables (Lachman, Orsák, & Pivec, 2000), thus the study of native berry fruits is of great economic sig- nificance since it can support the consumption and commercial activities. Chilean fruits such as arrayán, chequen, calafate, meli, maqui and murta (Fig. 1) are small pigmented native berries which were used as a food source since ancient times. At present, there is some regional use of berries from trees and shrubs belonging to Myrtaceae (Chilean myrtle, murta, arrayán, chequén, luma and meli), Berberidaceae (michay and calafate) as well as Eleaocarpa- ceae (maqui) occuring in south America. In Chile, ‘‘murtilla’’ (Myr- tus ugni Molina or Ugni molinae Turczaninov), is the best-known of the native Myrtaceae plants, where the people appreciate its red edible berries for its unique aroma. Infusions of the leaves of this species are anti-inflammatory and analgesic (Delporte et al., 2007) and the fruits contain several volatile compounds responsi- ble for the aroma (Scheuermann et al., 2008). Arrayán (Luma apicu- lata (DC.) Burret is an evergreen Myrtaceae tree of about 10 m in height with orange-red trunk and edible purple black berries, 1– 1.5 cm in diameter, ripe in early autumn and are half the size, more intense color but similar aspect and consistence than the world- wide commercialized blueberries (Vaccinium corymbosum) occur- ring in southern Chile and Argentina. Murillo (Murillo, 1889) describes the medicinal properties of Eugenia apiculata D.C., (a syn- onym for L. apiculata, (Hoffmann, 1995) as anti-inflammatory and balsamic. The fruits were used to prepare an aromatic liquor. The fruits of Luma chequén (Molina) A. Gray, syn: Myrceugenella che- quen (Mol.) Kaus are edible small berries with similar size than those of arrayán and murta. de Mösbach (de Mösbach, 1991) refer to L. chequen with uses in infusion and syrup as an astringent. Both L. apiculata and L. chequen fruits were used to prepare a South American native fermented beverage (Hoffmann, 1995). Calafate or Magellan barberry (Berberis microphylla G. Forst) is another http://dx.doi.org/10.1016/j.foodchem.2014.12.039 0308-8146/Ó 2014 Elsevier Ltd. All rights reserved. ⇑ Corresponding author. Tel.: +56 55 637229; fax: +56 55 637457. E-mail address: mario.simirgiotis@uantof.cl (M.J. Simirgiotis). Food Chemistry 176 (2015) 106–114 Contents lists available at ScienceDirect Food Chemistry journal homepage: www.elsevier.com/locate/foodchem