Chemistry
Food Chemistry 100 (2007) 13981401
www.elsevier.com/locate/foodchem
Laboratoire de Chimie des Plantes et de Synthe`se Organique et Bioorganique, Faculte des Sciences,
Universite Mohamed V-Agdal, BP 1014 RP, Rabat, Morocco
Scientic and Technical Services, University of Barcelona, Josep Samitier 1-5, Barcelona 08028, Spain
c
FRE2715, 51 rue Cognacg Jay, Reims 51100, France
Received 9 May 2005; accepted 17 November 2005
Abstract
Liquid chromatography (LC) coupled to negative electrospray ionization (ESI) tandem mass spectrometry (MS/MS) was used for the
sensitive identication of phenolic compounds in argan fruit pulp. Sixteen compounds were identied, mainly avonoid glycosides and
avonoid aglycons.
2006 Elsevier Ltd. All rights reserved.
Keywords: Argania spinosa; Argan tree; Flavonoid; Tandem mass spectrometry; Phenolic, Morocco
1. Introduction
The argan tree (Argania spinosa (L.) Skeels) of the family sapotaceae, is endemic in southwestern Morocco. Argan
seed, that contains the kernels used for the preparation of
the well-known edible argan oil, is covered by a milky pulp
sheathed by a particularly thick peel. Argan oil is exclusively prepared in Morocco and it has for a long time only
been sold on the Moroccan market. Nowadays, because of
dramatic improvements brought to its preparation (Charrouf, Guillaume, & Driouich, 2002), its high dietetic value
(Charrouf & Guillaume, 1999), and its general benecial
eect on human health (Charrouf & Guillaume, 1999),
argan oil is found in all industrialized countries. As the
pulp of the argan fruit is palatable to cattle and provides
a cheap protein-rich material for goats and other farm animals, its agricultural impact is of importance. Chemical
analysis of argan fruit pulp has already shown the presence
*
Corresponding author. Tel.: +212 376 828 48; fax: +212 377 132 79.
E-mail address: zcharrouf@menara.ma (Z. Charrouf).
0308-8146/$ - see front matter 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.foodchem.2005.11.031
acid (analytical grade) was from Merck (Darmstadt, Germany). Ultrapure water (Milli-Q, Waters, Milford, MA)
was used. Phenolic standards were purchased from Extrasynthe`se (Genay, France). The standard purity was above
98% and all of them were prepared as stock solutions at
1 g/L in methanol. Dilution of stock solutions with LC
mobile phase furnished working standard solutions
(1 mg/L).
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Table 1
Phenolic compounds identied in argan fruit pulp
Compound (%)a
Peak
tR (min)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
0.82
1.44
4.06
7.13
7.65
7.67
10.87
11.19 or 11.43
11.46
11.70
12.33
12.69
13.37
17.83
17.94
18.51
[MH]
Fragments
169
153
289
577
289
579
609
609
463
463
433
433
623
301
285
271
125
109
463, 301
MS/MS experiments
Neutral loss scan
308
308
162
162
132
162
308
Product ion
289
245
289
579
609
609
463
463
433
433
623
301
245
289, 245
301
301
301
301
301
271
315
151, 121, 107
271
119,109
at m/z 301). However, further investigations will be necessary to fully assess the exact structure of these compounds.
3.3. Flavonoid glycosides
Flavonoid O-glycosides, such as quercetin-3-O-galactoside (hyperoside) (9), quercetin-3-O-glucoside (isoquercetin)
(10), and naringenin-7-O-glucoside (12) were identied by
comparison of their retention time (11.46, 11.70, and
12.69 min, respectively) with that of reference substances
and by MS/MS analysis in neutral loss of 162 amu (loss of
tetrahydroxylated hexose) (Sanchez-Rabaneda et al., 2003;
Sanchez-Rabaneda et al., 2004). MS/MS analysis in neutral
loss of 132 amu (loss of trihydroxylated pentose) revealed
the presence of one avonoid glycoside having a pentose
within its structure (11, retention time 12.33 min). its ion
fragments were observed at m/z 433 and 301 in full scan
mode. To elucidate the aglycone, a product ion scan of m/
z 301 was performed. The observed fragment ions at m/z
151 and 121 evidenced that the aglycone of 11 was quercetin.
From its retention time, compound 11 was identied as
quercetin-3-O-arabinose, a compound that we already identied in a recent study (Sanchez-Rabaneda et al., 2003).
3.4. Other phenolic compounds
The avonoid aglycones catechin (3), epicatechin (5),
procyanidin (6), quercetin (14), luteolin (15), and naringenin (16) were identied by comparison with a standard.
Procyanidin (8) was identied by product ion scan
experiments.
Among the 16 compounds identied in the pulp of argan
fruits, only compounds 3, 5, and 7 had been previously
identied (Chernane et al., 1999). However, the presence
of p-hydroxybenzoic acid (Chernane et al., 1999) could
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