Food Chemistry 221 (2017) 123–129

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Food Chemistry
journal homepage: www.elsevier.com/locate/foodchem

Thermal stability of oils added with avocado (Persea americana cv. Hass)
or olive (Olea europaea cv. Arbequina) leaf extracts during the French
potatoes frying
Paula Jiménez a,⇑, Paula García a, Andrés Bustamante b, Andrés Barriga c, Paz Robert d
a
Depto. de Nutrición, Facultad de Medicina, Universidad de Chile, Santiago, Chile
b
Centro de Estudios Postcosecha, Facultad de Ciencias Agronómicas, Universidad de Chile, Santiago, Chile
c
Unidad de Espectrometría de Masas, Facultad de Ciencias Químicas y Farmacéuticas, Universidad de Chile, Santiago, Chile
d
Depto. Ciencia de los Alimentos y Tecnología Química, Facultad de Ciencias Químicas y Farmacéuticas, Universidad de Chile, Santiago, Chile

a r t i c l e i n f o a b s t r a c t

Article history: Effect of the addition of avocado (Persea americana cv. Hass) or olive (Olea europaea cv. Arbequina)
Received 28 April 2016 hydroalcoholic leaf extracts (AHE and OHE, respectively) on thermal stability of canola oil (CO) and high
Received in revised form 7 October 2016 oleic sunflower oil (HOSO) during French potatoes frying at 180 °C was studied. The extracts were
Accepted 11 October 2016
characterized by the total phenolic content, phenol chromatographic profiles and antioxidant activity.
Available online 12 October 2016
B-type trimer procyanidins were the major phenolic compounds identified in AHE. OHE showed higher
phenol content, antioxidant activity regarding AHE. CO + OHE and HOSO + OHE decreased the formation
Keywords:
of polar compounds and showed an anti-polymeric effect with respect to oils without extracts, whereas
Olive leaf
Avocado leaf
AHE extract showed a prooxidant effect on HOSO. Therefore, OHE showed an antioxidant effect on HOSO
Thermal stability and CO under the studied conditions. In addition, all systems (CO + AHE, HOSO + AHE, CO + OHE and
Frying HOSO + OHE) increased the retention of tocopherols. These results demonstrate the potential utility of
Antioxidants OHE as natural antioxidant for oils.
Ó 2016 Elsevier Ltd. All rights reserved.

1. Introduction are thermally unstable at temperatures above 140 °C, having a

Deep-fat frying (DFF) is a process of cooking in which a food is
immersed within edible oil or fat that serves as a heat-transfer
medium. During DFF process, oil is exposed to high temperature
in the presence of air and moisture. Under these conditions,
various chemical reactions can take place, such as: oxidation,
hydrolysis and polymerization (Dobarganes, Pérez-Camino, &
Márquez-Ruiz, 1988). These thermoxidative reactions are respon-
sible of the desirable flavor, color and texture of the fried food, as
well as, of the formation of undesirable constituents, such as polar
compounds.
Antioxidants are compounds that extend the induction period
of lipid oxidation or slow down the oxidation rate. For many years,
synthetic antioxidants have been used to improve the oxidative
stability of oils. However, in the last years there is a global trend
toward to addition of natural antioxidants (tocopherols and
polyphenols) from plant extracts. In spite of a high antioxidant
activity of the tocopherols has been reported in oil systems, they
⇑ Corresponding author.
E-mail address: paulajimenez@med.uchile.cl (P. Jiménez).
limited protection during frying process (Fusakawa, Kanda, &
Hara, 2009), whereas polyphenols have showed higher antioxidant
activity than tocopherols in high temperature oil systems because
polyphenols are located at the air-oil interphase (Orozco-Solano,
Priego-Capote, & Luque de Castro, 2011).
Plant extracts can be obtained from leaves, fruits, flowers, bark,
seeds and by-products. The effect of plant polyphenol-rich extracts
on thermal stability in vegetable oils at deep-fat frying tempera-
ture (>180 °C) has been evaluated for some plant extracts such
as: rosemary (Rosmarinus officinalis) and sage (Salvia officinalis)
(Che Man & Jaswir, 2000), oregano (Origanum vulgare) (Houhoula,
Oreupoulou, & Tzia, 2003), pomegranate (Punica granatum) (Iqbal,
Haleem, Akhtar, Zia-ul-Haq, & Akbar, 2008), curcuma (Curcuma
longa) and inca muña (Clinopodium bolivianum) (Chirinos,
Huamán, Betalleluz-Pallardel, Pedreschi, & Campos, 2011).
However, the results has been highly variable because of there
are many factors involved in the thermal stability of vegetable oils
such as: antioxidant nature (plant species, polyphenol profile
(extraction method, concentration extract), poor lipophilic of
antioxidative phenolics constituents, nature of oil nature (unsatu-
ration grade of oil), temperature and method for determining lipid

http://dx.doi.org/10.1016/j.foodchem.2016.10.051
0308-8146/Ó 2016 Elsevier Ltd. All rights reserved.
124 P. Jiménez et al. / Food Chemistry 221 (2017) 123–129

oxidation (polar compounds, peroxide value, conjugated dienes Table 1

and trienes), among others. Composition and initial characteristics of HOSO and CO oils.

Nowadays, several by-products are considered a valuable HOSO CO

source of polyphenols. In this context, avocado (Persea americana) Methyl esters (%)
and olive leaves (Olea europaea), have been widely used for cen-
C16:0 4.4 ± 0.13.9 6.2 ± 0.5
turies in ancient cultures or folk medicine, generally as infusions C18:0 3.1 ± 0.1 2.9 ± 0.1
with therapeutic properties (Owolabi, Jaja, & Coker, 2010). In avo- C18:1 w9 82.5 ± 2.2 53.4 ± 0.8
cado leaves, a wide polyphenol profile has been reported (caffeic, C18:2 w6 6.4 ± 0.4 20.4 ± 0.7
chlorogenic, coumaric, ferulic, gallic, hydroxybenzoic, protocate- C18:3 w3 0.3 ± 0.01 7.9 ± 0.4
a-Tocopherol 572.9 ± 19.4 212.3 ± 17.8
chuic, pyrocatechuic, resorcylic, sinapic, syringic and vanillic acids
c-Tocopherol nd 385 ± 2.3
and some flavonoids as apigenin, isorhamnetin, kaempferol 3-O- Total (mg/kg) 572.9 597.3
arabinopyranoside, kaempferol 3-O-b-glucopyranoside, kaemp- Polyphenols (lg CAE/g oil) 2.72 ± 0.42 3.15 ± 0.23
ferol 3-O-rhamnopyranoside, luteolin, luteolin 7-O-glucoside, PV (mEqO2/kg oil) 2.2 1.5
PC (%) 4.4 5.7
rutin, quercetin, quercetrin, quercetin 3-O-arapyranoside, querce-
tin 3-O-b-glucopyranoside, quercetin 3-O-b-D-glucoside, catechin nd: not detected; CAE: caffeic acid equivalent; PV: peroxide value; PC: polar com-
and epicatechin) (Ding, Chin, Kinghorn, & D’Ambrosi, 2007; pounds; HOSO: high oleic sunflower oil; CO: canola oil.
Owolabi et al., 2010). To our knowledge, the information about
the effect of olive and avocado leaf extracts on vegetable oils stabil- 2.1.3. Oil samples
ity at deep-frying is scarce. Terasawa, Sakakibara, and Murata High oleic sunflower oil (HOSO) and canola oil (CO) both with-
(2006) found that the addition of aqueous avocado epicarp extract out synthetic antioxidants were supplied from Camilo Ferrón S.A.,
to linoleic acid inhibited its oxidation during heating at 180 °C. (Santiago, Chile). The composition and initial characteristics of
However, the effect of avocado leaf extracts on thermal stability HOSO and CO are shown in Table 1.
of oils at 180 °C has not yet been reported.
On the other hand, in olive leaves, oleuropein is one of the 2.2. Preparation of avocado or olive leaves hydroalcoholic extracts
major phenolic compounds (19% w/w) (Xie, Huang, Zhan, &
Zhang, 2015). Other polyphenols have also been reported such 2.2.1. Avocado hydroalcoholic extract (AHE)
as: verbascoside, oleuroside, ligstrosides, apigenin, quercetin, Collected avocado leaves (11 kg) were scalded in water at
kaempferol, hesperitin, luteolin, ferulic, caffeic, p-coumaric, 95 °C  4.5 min. Then, the leaves were dried at 45 °C  18 h in a
chlorogenic and vanillic acids, luteolin-7-glucoside, apigenin-7- forced air oven (Memmert Model UFE 500, Germany). Dry avocado
glucoside, rutin, apigenin-7-rutinoside, luteolin-7-rutinoside and leaves (750.31 g) were ground and macerated in ethanol:water
luteolin-4-glucoside (Chiou et al., 2007; Salta, Mylona, Chiou, (50:50 v/v) (3 L) for 24 h at room temperature and then the extract
Boskou, & Andrikopoulos, 2007). Olive leaf extracts have been was obtained by filtration in Büchner funnel. This process was
added to olive, sunflower, palm, soybean oils and shortening dur- performed three times (second and third extraction with 2.5 L each
ing potatoes frying process (deep frying or pan-frying) at 180 °C one). The filtrates were combined and concentrated in a rotary
(Chiou, Kalogeropoulos, Efstathiou, Papoutsi, & Andrikopoulos, evaporator (Büchi, Flawil Switzerland) at 40 °C and filled up to final
2013; Chiou, Kalogeropoulos, Salta, Efstathiou, & Andrikopoulos, volume of 1.5 L with ethanol:water (50:50 v/v). The AHE extract
2009; Chiou et al., 2007; Zribi et al., 2013), showing in some cases were stored at 20 °C until analysis.
an increase in oxidative stability of those oils and a gradual
decreased of oleuropein. Oleuropein consists of three subunits: 2.2.2. Olive hydroalcoholic extract (OHE)
hydroxytyrosol, elenolic acid and a glucose molecule. Hydrolysis It was elaborated according to the method described by
of oleuropein to hydroxytyrosol has been reported at high Jiménez, Masson, Barriga, Chávez, and Robert (2011).
temperature, being the hydroxytyrosol a molecule known by its
antioxidant activity, and thermal stability (Yuan, Wang, Ye, Tao, 2.3. Characterization of avocado or olive leaves hydroalcoholic extracts
& Zhang, 2015). Therefore, oleuropein could to be an efficient
antioxidant in lipid matrices submitted at high temperatures. 2.3.1. Total polyphenol content (TPC)
The aim of this work was to evaluate the effect of the addition of TPC was determined using a colorimetric assay with Folin-
hydroalcoholic leaf extracts of avocado (AHE) or olive (OHE) on the Ciocalteu phenol reagent according to Singleton and Rossi (1965).
thermal stability of vegetable oils with different unsaturation The absorbance of samples was measured at 725 nm and the
degree (canola oil (CO) and high oleic sunflower oil (HOSO) during results were expressed as caffeic acid equivalents (CAE)/g fresh
French potatoes deep frying at 180 °C. weight (FW), according to a calibration curve (85.9–700.2 lg/mL,
R2: 0.9955). All experiments were performed in triplicate.
2. Materials and methods
2.3.2. Antioxidant activity (AA)
2.1. Materials The scavenging activity against 2,2-diphenyl-1-picrylhydrazyl

radicals (DPPH ) was performed spectrophotometrically (Unicam
2.1.1. Leaf samples UV/Vis ATI UNICAM, Cambridge, UK) according to the method
Olive (O. europaea cv. Arbequina) leaves were collected in described by Brand-Williams, Cuvelier, and Berset (1995). The
November–December 2013 from Millantú farm (Talagante, Región absorbance of the samples was measured at 517 nm by triplicate.
Metropolitana, Chile). Avocado (P. americana cv. Hass) leaves were The results were expressed as the extract concentration that
collected in January 2014 from Desarrollo Agrario farm (Llay-Llay, provided 50% inhibition (IC50).
Región de Valparaiso, Chile).
2.3.3. Liquid chromatography with mass spectrometry (LC–MS) of AHE
2.1.2. Potatoes The analyses were conducted using an Agilent 1100 HPLC
Fresh potatoes (Solanum tuberosum L. cv. Panda), cut into pieces (Agilent Technologies Inc., CA, USA) system coupled with an
of 8 mm  8 mm  100 mm (French potatoes), without antioxi- Esquire 4000 ion trap LC/MS system (Bruker Daltoniks, Germany),
dant treatments were obtained from Pat Fer Ltda. (Santiago, Chile). using a C18 column (5 lm, 4.6 mm i.d  25 cm, Spherisorb ODS-2,
 P. Jiménez et al. / Food Chemistry 221 (2017) 123–129 125

Waters, Ireland). The mobile phase was formic acid in water
(0.34% v/v, solvent A) and acetonitrile (solvent B) at a flow rate
of 1 mL/min according to the following elution gradient:
0–3 min, 7.3% B; 3–73, 7.3% B; 73–80 min, 35% B; 80–85 min,
70% B; 85–88 min, 70% B; 88–90 min, 7.3%. The total analysis time
was 90 min, and 5 min was required for reestablishing and equili-
brating the initial conditions. Phenolic compounds were detected
at 280 nm. The mass spectral data were acquired in negative mode;
ionization (nebulization) was performed with nitrogen as drying
gas at 50 psi, 365 °C and at a flow rate of 10 L/min and capillary volt-
age 3000 V. All scans were performed in the range 50–1400 m/z.
The trap parameters were set in ion charge control using manufac-
turer default parameters. Collision induced dissociation (CID) was
performed by collisions with the helium background gas present
in the trap. Fragmentation was set with Smart Frag.
2.4. Extract adding to frying oils
AHE or OHE were added to HOSO or CO (2000 g) at a concentra-
tion of 630 mg caffeic acid equivalent/kg oil. To improve the
extracts dispersion in oils, Tween-80Ò (0.1% v/v) (Sigma-Aldrich,
Missouri, USA) was added and then homogenized at 9500 rpm
for 2 min with a Polytron PT 2100 (Kinematica AG, Luzern,
Switzerland).
2.5. Frying assays
Six experimental oil systems were studied (HOSO + OHE,
CO + OHE, HOSO + AHE, CO + AHE, HOSO and CO). A domestic deep
fryer (Moulinex, France) was used considering a 0.24 surface/vol-
ume ratio. Oils (HOSO or CO) were heated at 180 ± 1 °C during
8 h per day. This process was repeated for 7 days to reach 56 h of
heating. The frying of potatoes (100 g) was performed by 5 min
every 1 h (8 frying cycles per day) reaching 4.7 h of frying at the
end of the process, without oil replenishment. After every day of
heating, oil samples (25 mL) were collected and stored at 20 °C
for subsequent tocopherol and polar compounds analysis.
Experiments were performed in triplicate.
2.6. Analytical methods
2.6.1. Polar compounds analysis
Polar compounds (PC) were determined by adsorption column
chromatography (IUPAC, 1992), and the distribution of PC by
high-performance size exclusion chromatography (HPSEC). HPLC
system consisted of a Merck-Hitachi L-6200A pump with a 20 lL
injection loop and a Merck RI-71 refractive index detector. The sep-
aration was performed on two in series 500 and 100 Å columns
(PLGEL, 5 lm, 0.8 cm i.d.  30 cm; Hewlett-Packard, Amherst,
MA). The mobile phase was tetrahydrofuran at a flow rate of
1 mL/min. Quantitative results were based on peak areas assuming
equal detector response.
2.6.2. Tocopherol analysis
Tocopherols were determined according to AOCS method
(1997) by HPLC using a LiChroCART Superspher Si-60 column
(5 lm, 4 mm i.d.  25 cm; Merck, Darmstadt, Germany); the
mobile phase was hexane: 2-propanol (99.5:0.5 v/v) at a flow rate

Table 2
Identification of phenolic compounds of AHE by LC–MS.

Peak Compound Precursor (m/z) Fragments MS2 (m/z)

3 Caffeic acid 181.8 164.5 135.6
7 Chlorogenic acida 337.4 162.6 134.6
9 Chlorogenic acida 355.0 162.5 144.5
11 B-type procyanidin dimer 577.5 409.1 451.0 425.0 559.0 289.0 246.9
14 B-type procyanidin dimer 577.9 451.0 425.0 559.1 409.1 397.1 288.9 437.0
15 B-type procyanidin trimer 867.1 579.0 577.1 409.2 427.1 451.0 288.9 697.1
16 A-type procyanidin dimer 577.5 451.0 409.2 425.0 289.0 246.8 541.2
17 B-type procyanidin trimer 867.0 578.9 577.2 451.1 427.1 409.1 291.0 714.9
18 B-type procyanidin dimer 578.8 427.0 409.1 451.0 291.0 246.9 559.0
19 A-type procyanidin dimer 577.8 451.0 425.1 409.1 559.0 289.0 246.9
21 B-type procyanidin trimer 866.4 577.0 451.1 409.2 559.1 738.8 712.9
26 A-type procyanidin dimer 577.7 450.9 409.1 559.0 425.0 288.9 246.9
27 B-type procyanidin trimer 866.6 577.1 451.1 409.2 289.0
30 B-type procyanidin trimer 866.5 577.1 451.1 409.2 289.0 715.1
31 Quercetin-O-dihexoside 627.0 303.0 464.9
33 B-type procyanidin trimer 865.5 577.0 451.1 409.1 559.1 695.1 713.1 739.0
Quercetin 302.7 138.5 282.9 284.9 256.9 190.6 228.8 164.5
36 Quercetin-O-pentohexoside 596.8 303.0 464.8
38 B-type procyanidin dimer 578.5 490.1 427.0 451.0 559.0 425.1 289.0 291.0
40 Quercetin-O-rutinoside 610.8 303.0 464.7
41 Quercetin-O-glucuronide 479.0 303.0
Quercetin-O-hexoside 464.9 303.0
42 Quercetin-O-hexoside 464.9 303.0
43 B-type procyanidin dimer 579.8 427.0 409.1 450.9 290.9 559.0
44 A-type procyanidin dimer 577.8 451.0 559.0 409.2 425.1 289.0 246.9
Dicaffeoylquinic acid 499.3 319.0 162.6
45 Quercetin-O-malonyl glucoside 551.3 303.0 533.0
46 Kaempferol-O-hexoside 449.4 286.9
47 B-type procyanidin dimer 578.5 409.1 427.0 450.9 559.0 289.0 300.9
Kaempferol-O-glucuronide 463.2 287.0
49 Kaempferol-O-malonyl hexoside 535.1 287.0 517.1
Isorhamnetin-O-glucuronide 493.0 317.0
50 Kaempferol-O-glucosyl ramnoside 594.9 433.1 287.0 415.1 397.1
A-type procyanidin dimer 577.8 451.0 559.0 409.1 425.0 288.9 246.9
51 B-type procyanidin dimer 578.4 409.1 451.0 559.0 425.1 289.0 246.9
Kaempferol-O-malonyl hexoside 535.1 286.9 517.1
57 Kaempferol-O-cumaroyl glucoside 595.2 308.9 287.0 575.5
a
Peaks 7 and 9 were identified both as chlorogenic acid; peak 7 the m/z signal for precursor corresponded to dehydrated and protonated form ([M-H2O+H]+) and peak 9
the m/z signal corresponded to protonated form ([M+H]+).
126 P. Jiménez et al. / Food Chemistry 221 (2017) 123–129
of 1 mL/min. The HPLC system consisted of a Merck-Hitachi
L-6200A pump with a 20 lL injection loop, and a Merck-Hitachi
F-1050 fluorescence detector coupled at a computer equipped with
the Clarity software. Peaks were detected at 290 and 330 nm
(excitation and emission wavelengths, respectively). Tocopherols
were identified and quantified using as external standards
(Calbiochem, Merck, Darmstadt, Germany).
The tocopherols data were fitted to first order kinetic model, ln
C = ln Co k(t), where C is the tocopherol concentration at time t,
C0 is the initial concentration of tocopherol (mg tocopherol/kg oil),
k is the degradation rate constant, and t is the frying time.
Degradation rate constants (k) were obtained from the slope of a
plot of the natural log of the tocopherols retention percentage vs.
time.
2.7. Statistical analysis
To determine the statistical differences in the polyphenol con-
tent, antioxidant activity and polar compounds content a one
way analysis of variance (ANOVA) was performed using Statgraph-
ics software, version 7.0 (Manugistics Inc., Statistical Graphics
Corporation, Rockville, MD).
3. Results and discussion
3.1. Characterization of extracts from avocado and olive leaves
The TPC of AHE reached a value of 3.7 ± 0.1 mg CAE/g leaf FW,
lower than those reported by Torres, Mau-Lastovicks, and
Rezaaiyan (1987) of 17.5–19.3 mg gallic acid equivalent (GAE)/g
leaf FW. The TPC of OHE was 6.5 ± 0.02 mg CAE/g leaf FW, similar
to the values found previously by our group (8.8 ± 0.07 mg CAE/g
leaf FW) (Jiménez et al., 2011) and by Le Floch, Tena, Ríos, and
Valcárcel (1998) (7.6 mg CAE/g leaf). Lower values (0.215, 1.77
Fig. 1. HPLC-UV chromatograms at 280 nm of AHE.
and 1.35 mg CAE/g leaf FW) were reported by Farag, Mahmoud,
and Basuny (2007), Salta et al. (2007) and Chiou et al. (2007),
respectively.
The AA of AHE and OHE were 0.11 ± 0.006 mg/mL and
0.01 ± 5.9  10 5 mg/mL, respectively. The AA of OHE was higher
than that reported by Kaeidi et al. (2011) (0.231 mg/mL extract)
and similar to Jiménez et al. (2011) (0.026 ± 10 5 mg/mL), being
this high AA attributed to oleuropein content (Hayes, Allen,
Brunton, O’Grady, & Kerry, 2011). For both extracts, the AA would
be attributed mainly to polyphenols and minor compounds
different to the tocopherols, as these were not present in the
extracts (data not shown).
The identification by LC–MS of AHE was achieved by comparing
m/z signals and fragment ions of each polyphenol with those
described in literature as it is shown in Table 2 and Fig. 1 (UV chro-
matogram). The main compound identified by LC–MS was B-type
trimer procyanidin (peak 15, 38.5%). Other compounds identified
in lower percentages were quercetin-O-glucoronide or quercetin-
O-hexoside (peak 41, 5.6%), quercetin-O-pentohexoside (peak 36,
4.0%), B-type dimer procyanidin (4.0%), caffeic acid, and chloro-
genic acid. Phenolic acids and glycosylated flavonoids have been
reported in avocado leaves (Lima et al., 2012; Owolabi et al.,
2010), whereas procyanidins (monomers to polymers) have been
reported in seed and peel of avocado (Kosinska et al., 2012;
Wang, Bostic, & Gu, 2010). Besides, our data show that a low
percentage of procyanidins in AHE could contain A-type linkage,
similarly as was described in avocado seed and peel by Wang
et al. (2010). In OHE we previously reported that the main com-
pounds identified were oleuropein and its derivatives, oleuroside
and oleuroside-10-carboxylic acid (Jiménez et al., 2011).
Differences in TPC, AA and polyphenol profiles of AHE or OHE
with the literature could be attributed to agronomical and techno-
logical factors such as: cultivar, leaf stage, season of harvest, geo-
graphical origin, and type of extraction methods (Naczk &
Shahidi, 2006).
 P. Jiménez et al. / Food Chemistry 221 (2017) 123–129 127

3.2. Frying tests followed first-order kinetics. The correlation coefficient (r2) was
used to determine the order of reaction (0.94–0.99).
AHE and OHE were added to oils (HOSO and CO) to evaluate the As was expected, the control systems (CO and HOSO without
thermal stability of vegetable oils during French potatoes deep fry- added extract) not showed significant differences on the PC
ing at 180 °C. The hydrophilic nature of polyphenols is a drawback (4–5%) at the beginning of frying process. However, at 56 h of
to their application in frying oils. Thus, in this study Tween-80Ò frying, HOSO (29%) had a lower PC percentage than CO (35%).
(0.1% v/v) was added as surfactant to improve the poor dispersal a-Tocopherol in HOSO was depleted before 8 h of frying (8.55%),
of extracts in oils. whereas in CO, a and c-tocopherol were detected until 24 h
(19.8%) and 32 h (11.1%) of frying, respectively. In line,
a-tocopherol degradation rate constant in monounsaturated oil
3.2.1. PC and tocopherols evolution (HOSO) was higher than polyunsaturated oil (CO). These results
Fig. 2, shows PC and remaining tocopherol evolutions for HOSO show that the fatty acid and tocopherol profiles of oils can play
(A, B, C) and CO (D, E, F) systems without and with AHE or OHE an important role on the thermooxidative oil stability as was also
(630 mg CAE/kg oil), and Table 3 shows the tocopherol degradation reported by Barrera-Arellano, Ruiz-Méndez, Velasco, Márquez-
rate constant. In all systems the degradation of tocopherols Ruiz, and Dobarganes (2002) and Lampi and Kalman-Eldin (1998).

HOSO A
HOSO + AHE B
Remaining Tocopherols (%)

100 40

Remaining Tocopherols (%)

Polar Compounds (%) 100 40

Polar Compounds (%)

80 80
30 30
60 60
20 20
40 40
10 10
20 20

0 0 0 0
0 16 32 48 64 0 16 32 48 64
CP Hours CP Hours
α-T α-T

CO D
HOSO + OHE C
Remaining Tocopherols (%)

100 40
Remaining Tocopherols (%)

100 40

Polar Compounds (%)

Polar Compounds (%)

80
80 30
30
60
60 20
20 40
40
10
10 20
20
0 0
0 0 0 16 32 48 64
0 16 32 48 64 Hours
CP
CP Hours α-T
α-T γ -T

CO + AHE E
CO + OHE F
Remaining Tocopherols (%)

Remaining Tocopherols (%)

100 40 100 40
Polar Compounds (%)

Polar Compounds (%)

80 80
30 30
60 60
20 20
40 40
10 10
20 20

0 0 0 0
0 16 32 48 64 0 16 32 48 64
CP Hours CP Hours
α-T α-T
γ -T γ -T

Fig. 2. Polar compounds (PC) and remaining tocopherol (alpha and gamma) evolutions for HOSO (A,B,C) and CO (D,E,F) systems, during the frying potatoes french at 180 °C.
HOSO, high oleic sunflower oil; CO, canola oil; OHE: olive leaf hydroalcoholic extract; AHE: avocado leaf hydroalcoholic extract.
128 P. Jiménez et al. / Food Chemistry 221 (2017) 123–129

Table 3
Degradation rate constants (k), during frying french potatoes in HOSO and CO systems
at 180 °C.
1
System Kobs (h )
HOSO a-T >0.08
HOSO + OHE a-T 0.032 ± 0.007c
HOSO + AHE a-T 0.080 ± 0.005d
CO a-T 0.063 ± 0.005a
CO + OHE a-T 0.019 ± 0,001b
CO + AHE a-T 0.029 ± 0.005c
CO c-T 0.064 ± 0.005a
CO + OHE c-T 0.021 ± 0.001b
CO + AHE c-T 0.035 ± 0.003c

HOSO: high oleic sunflower oil; CO: canola oil; OHE: olive leaf hydroalcoholic
extract; AHE: avocado leaf hydroalcoholic extract; a-T: alpha tocopherol; c-T:
gamma tocopherol; nd: no detected. Different letters show significantly differences
among systems (p < 0.05).

When the tocopherols are depleted, the propagation phase

begins and the formation of polar compounds increases faster. At
the end of the study (56 h), PC formation percentage did not show
statistic differences between CO (35.2%) and CO + AHE (35.2%),
while in the CO + OHE (25.1%) system, the percentage was signifi-
cantly lower. In the case of HOSO, the system HOSO + AHE (34.2%)
increased PC formation regarding HOSO (29.8%). This would indi-
cate a pro-oxidant effect by the AHE extract in this oil under the
studied conditions. On the contrary, in the system HOSO + OHE
(25.2%) PC percentage was significantly lower regarding HOSO. In
spite of that the addition of AHE or OHE increased the remaining
of tocopherols in CO and HOSO during the frying, the degradation
rate constants were lower for systems with OHE, explaining thus a
greater protective effect of OHE on PC formation (Table 3). Other
studies have also reported a decrease in the formation of polar
compounds in edible oils added with rosemary polyphenolic
extract during heating at 180 °C (Casarotti & Jorge, 2014) and
during frying of potatoes with curcuma (Nor, Mohamed, Idris, &
Ismail, 2009) and inca muña extracts (Chirinos et al., 2011).
Rosemary extract was more efficient in delaying polar compounds
formation than tocopherol in a sunflower seed oil and palm olein
mixture, during deep frying of potato slices at 180 °C (Alizadeh,
Nayebzadeh, & Mohammadi, 2016).
In this study, the systems with OHE (HOSO + OHE and CO
+ OHE) showed a lower degradation rate constant of tocopherol
and PC formation than oils without OHE. This behaviour could be
attributed to higher AA, TPC and/or oleuropein (main polyphenol)
of the OHE. In addition, two alternatives could explain the higher
remaining tocopherols in oil systems with OHE: 1.-the polyphenols
may be degraded while tocopherols are still present or
2.-polyphenols in OHE may partly regenerate the tocopherols, thus
resulting in a higher remaining of these compounds.
In the first case, when oleuropein from OHE vs procyanidins
from AHE are added to a lipid systems, the degree of protection
against oxidation would depend on polyphenol structural features
(chemical reactivity towards peroxyl and other reactive species), as
was reported by Pedrielli and Skibsted (2002).
In the second case, there is some evidence of a greater antioxi-
dant effect when combinations of flavonoids and a-tocopherol
have been used in lipid models (Marinova, Toneva, & Yanishlieva,
2008; Pazos, Andersen, Medina, & Skibsted, 2007). It has been
suggested that the tocopherol could be regenerated from its toco-
pheroxyl radicals by some polyphenols (Pedrielli & Skibsted, 2002).
Thus, oleuropein could regenerate tocopherols but not procyanidins.
3.2.2. Distribution of PC
Distribution of PC in HOSO and CO submitted to French
potatoes frying at 56 h and 180 °C is shown in Fig. 3(A and B,
Fig. 3. Effect of addition of extracts (OHE or AHE) on alteration of polar species of
lipid systems (A: HOSO and B: CO) during the frying of french potatoes at 180 °C.
TGP: triacylglycerols polymers; TGD: triacylglycerols dimers, oxTG: oxidized
tryacylglycerols; DG: diacylglycerols; FA: fatty acid. HOSO, high oleic sunflower
oil; CO, canola oil; OHE: olive leaf hydroalcoholic extract; AHE: avocado leaf
hydroalcoholic extract.
respectively). Initially, before frying process, it was detected a
low amount of polar species including oxidized fatty acid (FA),
oxidized triacylglycerol (oxTG), triacyglycerol dimers (TGD) and
triacyglycerol polymers (TGP) (data not shown).
As can be seen, HOSO + AHE (3A) and CO + AHE (3B) not showed
differences on fraction of triacylglycerol polymers (TGP), whereas a
lower fraction TGP was obtained in the HOSO + OHE and CO + OHE,
all compared with its respective oil control. These results suggest
that polyphenols from OHE were able to act as anti-polymerizing
compounds in HOSO and CO at frying temperature. This behavior
could be explained by the mechanism of action of polyphenols as
antioxidants. Houhoula et al. (2003) suggested that these com-
pounds have the ability to donate hydrogen atoms to free radical
(peroxyl) formed during frying, preventing thermally induced
polymerization reactions. Besides, some studies reported that
oleuropein would be stable thermally. Chiou et al. (2013) reported
oleuropein retention ranged 3.4–12.2% in vegetable oils of different
unsaturation degree added with olive leaf extract after eight
successive deep frying cycles at 180 °C. Likewise, 30%
oleuropein retention in olive oil was obtained under similar condi-
tions (Andrikopoulos, Dedoussis, Falirea, Kalogeropoulos, &
Hatzinikola, 2002).
4. Conclusions
The addition of OHE to CO and HOSO decreased the polar
compounds formation which could be attributed to the protective
action of polyphenols (mainly oleuropein) and/or minor compo-
nents present in the extract. In spite of the addition of AHE and
OHE increased the retention of tocopherols in CO and HOSO, the
AHE did not show an antioxidant effect respect to oils control.
These results suggest the potential utility of OHE as natural
 P. Jiménez et al. / Food Chemistry 221 (2017) 123–129
antioxidant for oils, being necessaries further studies to improve
technological and sensory properties in order to develop a
commercial product.
Acknowledgments
This work was supported by FONDECYT-CONICYT project N
°11130373 (Chile, Prof. Paula Jiménez Patiño).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.foodchem.2016.
10.051.
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