Antioxidant and Metabolite Profiling of North American and Neotropical Blueberries Using LC-TOF-MS and Multivariate Analyses Chunhui Ma, † Keyvan Dastmalchi, † Gema Flores, †,‡ Shi-Biao Wu, † Paola Pedraza-Peñ alosa, § Chunlin Long, # and Edward J. Kennelly* ,†,# † Department of Biological Sciences, Lehman College, and The Graduate Center, The City University of New York, 250 Bedford Park Boulevard West, Bronx, New York 10468, United States ‡ Instituto de Fermentaciones Industriales, Consejo Superior de Investigaciones Científicas (CSIC), c/Juan de la Cierva 3, 28006 Madrid, Spain § Institute of Systematic Botany, The New York Botanical Garden, 2900 Southern Boulevard, Bronx, New York 10458, United States # College of Life and Environmental Sciences, Minzu University of China, 27 Zhong-guan-cun South Avene, Haidian District, Beijing 100081, China * S Supporting Information ABSTRACT: 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 V. corymbosum) 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. KEYWORDS: Ericaceae, blueberry, multivariate analysis, chemometrics, iron chelation, antioxidant markers ■ INTRODUCTION Metabolite fingerprinting has been used as an effective tool in comprehensive metabolite profiling for diverse applications such as disease diagnosis, toxicology, and drug discovery. 1 In the field of plant sciences, metabolite profiling was initially used to assess the relationship between global metabolite pool and specific environmental conditions or the impact of herbicide treatment. 2 Recently, metabolite profiling has been increasingly used in the area of phytomedicine to standardize botanical products or herbal medicines for their quality and safety. 2 However, correlating marker ions and biological activity using metabolite profiling has not been widely employed, especially in studies of edible or medicinal plants. A great deal of phytochemical and bioactivity research on Ericaceae has focused on temperate species of Vaccinium L., 3-6 which is only 1 of the 32 berry-producing genera within the tribe Vaccinieae of the plant family Ericaceae. 7,8 More than 600 different species of berry-producing Ericaceae are native to the New World tropics (neotropics). 7,8 Berries of several genera of neotropical blueberries are consumed raw or in different types of preparations, including those of several species in the genera here studied (Pedraza-Peñ alosa, personal correspondence). Perhaps the best example of a neotropical blueberry as a food source is some Vaccinium plant berries that are traditionally harvested for human consumption in several regions of South America. The growing interest in them has spurred a variety of enterprises experimenting with the development and commer- cialization of food products or the establishment of plantations; in many regions, the trade of these species has already moved from local markets to specialized supermarkets. Despite the potential, it must be also noted that the determination of the taxonomic identity of some species remains difficult, an important factor among dozens of potentially edible species with relatives with uninvestigated reports of toxicity (Pedraza- Peñ alosa, personal correspondence). Although the exploration of the uses of neotropical blueberries is an open and promising field, it should be undertaken with caution as the edibility and nutritional value of most of the species, including those in this study, remain poorly undocumented or at early stages. There are very few published accounts on the potential health benefits of neotropical relatives of blueberries. 9 In a previous study we Received: October 13, 2012 Revised: March 11, 2013 Accepted: March 19, 2013 Published: April 2, 2013 Article pubs.acs.org/JAFC © 2013 American Chemical Society 3548 dx.doi.org/10.1021/jf400515g | J. Agric. Food Chem. 2013, 61, 3548-3559