doi:10.1016/j.jfca.2007.04.012
Copyright © 2007 Elsevier Inc. All rights reserved.
Original Article
HPLC/DAD/ESI/MS detection of lignans from Spanish and Italian Olea europaea L. fruits
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Maria Jesus Oliveras Lópeza, Marzia Innocentib, Francesca Ierib, Catia Giaccherinib, Annalisa Romanib and Nadia Mulinaccib,
, 
aDepartment of Nutrition and Food Science, University of Granada, Campus Universitario de Cartuja, 18071 Granada, Spain
bDepartment of Pharmaceutical Science, University of Florence, Via Ugo Schiff 6, 50019 Sesto F.no (Firenze), Italy
Received 27 September 2006;
revised 6 April 2007;
accepted 19 April 2007.
Available online 30 June 2007.
Abstract
The aim of the present study was to verify the distribution of lignans in pulp and stones of olive fruits. Analyses were carried out by HPLC/DAD/MS on four cultivars: Frantoio and Taggiasca from Italy, Arbequina and Picual from Spain. The main results can be summarized as follows: (a) lignans were demonstrated to be present in the stone; (b) acetoxypinoresinol, pinoresinol, previously detected in the respective extra virgin olive oils, and OH-pinoresinol were found in the samples; (c) the total lignan content ranged between 0.1 and 0.29 mg/g of dried stone weight. These values agree with the average lignan content reported in literature for the respective extra virgin olive oils.
Keywords: Olive fruits; Acetoxypinoresinol; Stone; Italian and Spanish cvs; HPLC/DAD/MS; Lignan; Olive oil; Olive pit; Phytoestrogen
Fig. 1. Chemical structures of the investigated lignans.
Fig. 2. Applied procedures for the extraction of lignans from stones and pulp of Arbequina and Taggiasca fruits.
Fig. 3. Scheme of the extraction method that presents some similarities with the malaxation process, applied to olive pulp of Taggiasca.
Fig. 4. Chromatographic profile at 280 nm, TIC and EI profiles of the ether fraction from methanol extract at reflux from Taggiasca powdered stone: ion at m/z 357 and m/z 415, for Pr, and Ac–Pr, respectively.
Fig. 5. Chromatographic profile at 280 nm (a) of the methanol Taggiasca stone extract: ion at m/z 415 (b), m/z 373 (c), and m/z 357 (d), for Pr, Ac–Pr, and OH–Pr, respectively, are shown.
Fig. 6. MS spectra in negative ionization mode and fragmentor 100 V, of Ac–Pr (a), Pr (b), and OH–Pr (c).
Fig. 7. Flow chart on the products obtained from milling of the whole fruit and occurrence of lignans. The quantitative range for each cv has been extrapolated from the papers cited in the introduction.
Table 1.
Distribution of the three lignans in the stone extracts

The quantitative evaluation was carried out by ES/MS in negative ionization mode. These data are expressed as mg/g dried weight and they are an average of three determinations (% RSD below 10%).

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