Comparative Analysis of Olive Oil Organogels

Containing Beeswax and Sunflower Wax with

Breakfast Margarine
Emin Yılmaz and Mustafa Öğütcü

Abstract: The purpose of this research was to develop olive oil organogels with sunflower wax (SW) and beeswax (BW)
at 3%, 7%, and 10% addition levels and to compare these organogels with breakfast margarine (BM). The organogels
and BM sample were stored at 2 different temperatures (4 and 20 °C), and the peroxide values (PVs) and textural
properties were monitored for 3 mo. The PVs of all organogels were within legal limits and the gels were structurally
stable throughout the storage period. The textural properties of 3% SW and 7% BW organogels were closely similar to
BM. The solid fat contents of the organogels were lower than that of the BM. Moreover, the thermal properties of 3%
E: Food Engineering &
Physical Properties

BW gel were more similar to that of the BM. The results of X-ray diffraction peaks, approximately 3.70 and 4.10 Å,
were similar to β  polymorphic form. In conclusion, both of the organogel types may have value in replacing BMs.

Keywords: beeswax, enthalpy, organogel, storage, sunflower wax, X-ray diffraction

Practical Application: This study has proved that successful organogels of olive oil with beeswax and sunflower wax can
be produced. Organogels are plastic fats completely made with liquid oils and do not include either trans or saturated
fats. The margarine producers can adapt this technology to provide the healthy olive oil to the consumers in a spreadable
form.

Introduction produced (Toro-Vazquez and others 2007; Marangoni and Garti

Beeswax (BW) is an organic wax produced by bees from the
genus Apis mellifera L (Grant 2005). BW, recognized as E 901 too, is
an approved food additive worldwide and it is certified by Food &
Drug Administration (FDA Under Regulation 21 CFR 184.1973)
(EU 1995). BW is used in food industry as stabilizer, texturizer for
chewing gum bases, carrier for food additives (including flavors and
colors) and it also serves as clouding, glazing, and releasing agent
(EFSA 2007). Studies on BW have revealed that it consists of 70%
to 71% total esters, 1% to 1.5% free alcohols, 9% to 11% free acids,
and 12% to 15% hydrocarbons (Grant 2005; Bogdanov 2009).
Sunflower wax (SW) is a hard, crystalline, vegetable wax obtained
during the winterization of sunflower oil and has a high melting
point. It is known that SW contains long chains of saturated C-42
to C-60 esters derived from fatty alcohols and fatty acids (Hwang
and others 2012). SW can be used as emulsifier for creating new
textures due to its lipophilic characteristics. Therefore, SW can be
used for modifying the crystallization behavior of lipids (Kerr and
others 2011).
Recently, a new approach called as organogelation is developed
in order to prepare healthier products. Organogels are defined as
3-dimensional networks of an organic phase produced by adding
some organogelators into the liquid phase. When the organic
phase is edible oil, the structure is sometimes called as oleogel.
Organogels have some advantages such as not changing the fatty
acid composition; therefore, no trans and saturated fatty acids are Materials and Methods
2011; Co and Marangoni 2012).
In literature, many different kinds of waxes and oils have been
used for organogelation. Toro-Vazquez and others (2007) and
Morales-Rueda and others (2009) reported the thermomechani-
cal and rheological properties of safflower oil organogels prepared
with Candelilla wax. Dassanayake and others (2009) reported the
physical properties of salad oil (canola: soybean oil blends) and
olive oil (OO) organogels prepared with Candelilla, Carnauba,
and Rice bran waxes. In another study, the thermal and tex-
tural properties of SW–soybean oil organogels were investigated
(Hwang and others 2012). The minimum concentration required
for gel formation is determined for BW, but it does not include
detailed analyses (Hwang and others 2012). As a result, the investi-
gation of the storage stability of the developed organogels in these
studies was limited.
The actual target of this research was to improve OO organogels
with BW and SW. Furthermore, the physicochemical properties
of the organogel samples were investigated and their textural and
oxidative stability was also monitored during a storage period of
90 d at 2 different temperatures (4 and 20 °C). To the best of our
knowledge, this is the 1st report showing the comparison of BW
and SW as organogelators, and the organogels made thereof is also
compared with a commercial margarine for products properties.

Materials
MS 20140352 Submitted 3/4/2014, Accepted 6/16/2014. Authors are with OO was purchased from a local commercial market (Çanakkale,
Dept. of Food Engineering, Faculty of Engineering, Çanakkale Onsekiz Mart
Univ., 17020 Çanakkale, Turkey. Direct inquiries to author Yılmaz (E-mail: ey-
Turkey). Beeswax 8108 and sunflower wax 6607L were obtained
ilmaz@comu.edu.tr). from KahlWax (Kahl GmbH & Co., Trittau, Germany). BW
is classified as GRAS (generally recognized as safe) status food

C 2014 Institute of Food Technologists

 R

E1732 Journal of Food Science r Vol. 79, Nr. 9, 2014 doi: 10.1111/1750-3841.12561
Further reproduction without permission is prohibited
Olive oil organogels . . .

additive and is in solid pelleted form and white in color. SW is
solid yellowish pellet stated as safe for food uses by the manufac-
turer. Commercial margarine was purchased from a local market.
The composition of it was 59% vegetable oil blend (sunflower, cot-
tonseed, palm, canola, and safflower oils), water, skimmed pasteur-
ized milk, emulsifier (mono- and diglycerides and soy lecithin), salt
(0.2%), potassium sorbate, vitamins A and D, and β-carotene and
butter flavor. Total saturated fatty acids comprise 17 g/100 g with
0.59 g/100 g trans fatty acids. All of the chemicals used in the analy-
ses were of analytical grade and purchased from Merck (Darmstadt,
Germany) and Sigma-Aldrich (St. Louis, Mo., U.S.A.).
Preparation of the organogels
In order to form the organogels, previously weighed OO and
waxes were placed into separate pyrex glasses and heated in a water
left in water bath for 2 h at 90 °C for equal temperature setting.
Afterward, the tubes were left at room temperature to cool down
and for gel formation. Meantime, the time was recorded for each
sample. After rotating the tubes 90o and waiting until the flowing
stops, the elapsed time was recorded as gelation time (Dassanayake
and others 2009).
Solid fat content
The solid fat content (SFC) of the organogels was determined
by applying method ISO 8292 (ISO 2008) with Nuclear Magnetic
Resonance spectroscopy (NMR) device (Bruker NMR Analyzer
mq20 The Minispec, Bruker Optics, Inc., Billerica, Mass., U.S.A.).
The measurements of the organogel samples were performed at
2 different temperatures at 20 and 35 °C. The experiment was
carried out at 20 MHz proton resonance frequency at 20 °C. Pulse
sequence; shaped pulse, length 500 μs, phase 0o , attenuation 15

E: Food Engineering &

bath set to 90 °C. Next, completely melted BW (melting point 62

Physical Properties
to 65 °C) and SW (melting point 74 to 80 °C) were mixed with dB, wait for dead time, acquire data for 2 ms with max speed, and
OO and the mixture was stirred with a hand-operated kitchen phase 0o . The calibrations of the NMR device were done with
stirrer at isothermal conditions for 5 min. The wax addition levels the standard solutions including 0%, 31%, and 73.5% solid fat. The
were 3%, 7%, and 10% (w/w) for both waxes. The liquid mixture results are given as percentage of SFC.
was placed into sterile plastic cups (150 mL), Eppendorf, and glass
tubes (10 mL) with caps for further analyses. For the formation Thermal analysis
of the gels, the samples left at room temperature overnight. For All samples were analyzed with Perkin-Elmer Differential Scan-
the study of storage, the organogels filled in separate cups for each ning Calorimeter-4000 Series (DSC) (Groningen, The Nether-
month were stored in a dark place at room temperature (20 °C) lands). The instrument was calibrated with Indium in addition
and in a refrigerator (4 °C), and they were analyzed periodically. to Zinc. First, 5 to 7 mg of organogels was weighed in alu-
The study was repeated twice following the procedure explained minum pans and the pans were hermetically sealed. The sam-
above and each sample was analyzed in duplicate. The samples were ples were heated from 20 to 120 °C at 10 °C/min heating rate,
coded with 3 digits that the 1st letter designates olive oil (O), the and then, the samples were cooled to −20 °C at 10 °C/min
2nd letter is for the waxes (B or S), and 3rd letter shows the addition cooling rate and kept for 3 min at that temperature for the oc-
levels (3%, 7%, or 10%) of the organogelators. Accordingly, the currence of full crystallization. Finally, the samples were heated
sample codes are: OO—olive oil; BW—beeswax; SW—sunflower again to 100 °C at 5 °C/min heating rate. From the thermo-
wax; BM—commercial breakfast margarine; OB3, OB7, OB10 grams, the thermal parameters of the samples were calculated by
and OS3, OS7, OS10—organogels. the Pyris 1 Manager software of the instrument (Dassanayake and
others 2009).
Color measurement
The color of the organogel samples was measured with a Minolta Crystal morphology
CR-400 colorimeter (Konica Minolta Sensing, Osaka, Japan) with A sufficient amount of melted organogel sample was dropped
CIE lab standards. on a lam and covered with a lamel by 45° angle. The sample was
left for 1 h at room temperature for full gelation. Then, the polar-
Oil binding capacity ized light microphotographs (PLMs) were taken with an Olympus
The method of Da Pieve and others (2010) was adapted for BX51 polarized light microscope (Olympus Optical Co., Ltd.,
this analysis. First, empty Eppendorf tubes were carefully weighed Tokyo, Japan) equipped with a CCD (Canon, Tokyo, Japan) cam-
(a). Approximately, 1 mL of organogel sample was placed into an era. The PLM pictures were taken only for the fresh organogel
empty Eppendorf tube from the completely melted mixture and samples (Toro-Vazquez and others 2007; Dassanayake and
the tubes were left for 1 h for organogel formation in refrigerator. others 2009).
When the organogels were completely formed in the refrigerator,
the tubes were carefully weighed (b) and centrifuged at 9167 × g X-ray diffraction analysis
for 15 min at 20 °C. Then, the tubes were turned over and left for The X-ray diffraction (XRD) analyses of the samples were done
3 min for drainage of excess oil and then the tubes were weighed with Rigaku D-Max Rint 2200 model X-Ray Diffractometer
(c). Finally, the oil binding capacity (% OBC) was calculated by (Rigaku Int. Corp, Tokyo, Japan) at room temperature. The an-
Eq. (1). gular scans (2θ = 2.0 to 50° by 2°/min) were performed by using
a Cu source X-ray tube (λ = 1.54056 Å) at 40 kV and 40 mA.
%Rel e a s e d Oi l = [(b − a ) − (c − a )] / (b − a ) × 100 The data were analyzed with MDI Jade 7 Materials Data Inc.
(Livermore, Calif., U.S.A.) software program.
%OBC = 100 − %Rel e a s e d Oi l (1)
Texture analysis
The textural properties of the organogels were measured with
Crystal formation time a Texture Analyzer TA-XT2i (Stable Microsystems, Surrey, U.K.)
Approximately 10 mL of organogel samples were placed into equipped with 45° conic acrylic probe. The technique of “pene-
glass tubes from the completely melted mixture and the tubes were tration test” was selected for applying 3.0 mm/s penetration speed

Vol. 79, Nr. 9, 2014 r Journal of Food Science E1733

 Olive oil organogels . . .
into 23 mm depth of the sample, and then the probe was pulled
out from the sample at 10 mm/s speed. The textural properties
of the organogels were calculated via instrument software (Tex-
ture Exponent v.6.1.1.0, Stable Microsystems). Each month the
organogel samples in separate cups were stored at room tempera-
ture (20 °C) and in refrigerator (4 °C), and they were analyzed at
0th, 30th, 60th, and 90th d of storage (Moskowitz 1987).
Oxidative stability
The peroxide values (PVs) of the organogels were measured by
applying the method of Cd 8-53 (AOCS 1987) during 90 d of
storage period at both storage temperatures for each month.
Statistical analysis
The duplicate measurements within each replicate of organogel
E: Food Engineering &
Physical Properties
productions were performed for the samples and the results were
represented as mean values with standard deviations. The data
were analyzed by analysis of variance (Anova) and the multiple
comparisons of the means accomplished by Tukey’s test. Statistical
analysis was performed with Minitab v.16.1.1 (Minitab, 2010).
Results and Discussion
Physicochemical properties of the OO organogels
The physicochemical properties of the organogel samples mea-
sured in this study are presented in Table 1. L (luminosity), a∗
(+ redness/ – greenness), and b∗ (+ yellowness/ – blueness) val-
ues of the organogel samples are the color parameters. The L
values of the BW organogels ranged from 39.03 to 56.01, while
the L values of SW organogels varied between 48.70 and 65.78.
These results revealed that the L values increased with the increase
of wax concentrations for both organogel samples (P ࣘ 0.001).
Furthermore, similar results were observed for a∗ and b∗ values
of the BW and SW organogels (Table 1). L and a∗ values were
not affected by wax types, whereas b∗ values were affected (P ࣘ
0.001). Additionally, SW organogels were more luminous and yel-
lowish than BW organogels. On the other hand, L and a∗ values
of the BW and SW gels compared with the control sample (BM)
were significantly different (P ࣘ 0.001) (Table 1). Thus, b∗ val-
ues of the BW gels and BM sample were closely similar, while
the b∗ values of SW gels were significantly different from BM
sample (P ࣘ 0.001). These color differences between organogels
and control sample (BM) might be due to the processing methods
applied and the different ingredients used. It is well known that
margarine is an emulsion and contains certain amounts of water,
emulsifiers, colorants, vitamins, milk powder, and so on (O’Brien
2004), but the organogels do not contain water or any other in-
gredients. Nevertheless, margarine production techniques such as
hydrogenation, interesterification, and fractionation are chemical
processes, while organogelation is a physical process (Lupi and
others 2011). The other important physicochemical parameter of
the gels was OBC. As it is seen in Table 1, the OBC values of
all organogels were higher than 99%, and were not affected by
wax types and addition levels. This indicates that both of the
waxes are good enough in stable gel network formation. The
time required for crystal formation (CFT) of the BW and SW
organogels varied between 6.0 and 10 min and 3.5 and 5.0 min,
respectively. The CFT values of BW and SW were significantly
different (P ࣘ 0.001). These results revealed that SW exhibited
more rapid crystallization than BW in OO, while the minimum
gel formation concentrations of BW and SW organogels were 1%
(data not shown). Similar findings were observed by Hwang and
E1734 Journal of Food Science r Vol. 79, Nr. 9, 2014
others (2012). In addition, during this measurement, the previ-
ously formed organogels were melted in water bath and cooled
to ambient temperature for regelation to measure the CFT, and
this procedure permitted us to observe the phase behavior of the
organogels. There was no phase separation during this thermal cy-
cling. In fact, during the 3 mo storage period, there was no phase
separation, and the organogels were quite stable in their gelled
state.
SFC of edible oils and fats is a characteristic that defines the
percentage of the solid parts of fats at certain temperatures. SFC
values show the changes in consistency and plasticity of food prod-
ucts at different temperatures and SFC is an essential measurement
in bakery, confectionery, and margarine industries (Augusto and
others 2012). The SFC values of BW organogels ranged from
2.06% to 7.14% at 20 °C and from 1.53% to 5.56% at 35 °C
(Table 1). On the other hand, the SFC values of SW organogels
varied among 2.20% and 6.76% at 20 °C, and 2.21% and 7.17% at
35 °C. Furthermore, the SFC values of both organogel types were
found to increase with the increase of wax contents (P ࣘ 0.001)
(Table 1). From the data presented in Table 1, it was found out
that SW and BW organogels had similar SFC values at 20 and
35 °C. Chopin-Doroteo and others (2011) reported that the SFC
value of the safflower organogel prepared with 3% candelilla wax
was 2.25%. These results are in line with our findings, while the
SFC values of the BM sample were 7.70% at 20 °C and 1.63% at
35 °C. Whereas, the control sample (BM) was quite different and
showed higher SFC than the organogel samples (P ࣘ 0.001) (Ta-
ble 1). Karabulut and others (2003) reported that the SFC values
of hydrogenated fats increased with fat saturation degree. Also, in
the same study, it was reported that the SFC values increased with
the increase in the concentration of long chain fatty acids and the
formation of saturated and trans fatty acids.
Thermal behavior of the OO organogels
The thermal parameters of BW and SW organogel samples are
given in Table 2. The crystallization temperatures of OO, BW,
and SW were −17.19, 58.28, and 69.27 °C, and their crystal-
lization enthalpies were −6.15, −171.29, and −197.40 J/g, re-
spectively. The melting temperatures of OO, BW, and SW were
−3.96, 63.15, and 76.29 °C and their melting enthalpies were
71.36, 174.44, and 199.68 J/g, respectively. These results indi-
cated that SW has higher melting temperatures and enthalpies
than BW (P ࣘ 0.001). Similar results were detected for both types
of organogels (Table 2). Accordingly, the crystallization temper-
atures of BW organogels ranged from 35.06 to 43.79 °C, while
the melting temperatures ranged from 44.36 to 50.08 °C. Nev-
ertheless, the crystallization and melting temperatures of the SW
organogels were between 51.53 to 58.63 °C and 58.26 to 63.59 °C,
respectively. As can be seen in Table 2, the melting and crystalliza-
tion points of BW and SW organogels were significantly different
from each other (P ࣘ 0.001). As expected, the melting tempera-
ture of the organogels was found to depend on wax addition level
(Table 2). Besides, both types of organogels were thermoreversible
gels, and there was no phase separation during the thermal cycling.
In previous studies, different results were obtained for organogels
prepared with different waxes. Hwang and others (2012) reported
that the melting temperatures of soybean organogels prepared with
SW varied from 47.00 to 65.00 °C and their enthalpies ranged
from 0.20 to 15.00 J/g at 0.50% to 10.00% addition levels, re-
spectively. These findings are consistent with our results. On the
other hand, the melting temperature of BM was 40.36 °C. Despite
being statistically different, the melting points of BW organogels
Olive oil organogels . . .

Table 1–The color (L, a∗ , and b∗ ) values, oil binding capacity (OBC), crystal formation time (CFT), crystal size (Å), and solid fat
content (SFC) of BW and SW organogels (Mean±Sd).

Sample L a∗ b∗ OBC (%) CFT (min) Crystal Size (Å) % SFC (20 ˚C) % SFC (35 ˚C)
OB3 39.03 ± 0.09Ae −4.36 ± 0.14Bc 10.96 ± 2.10Bc 99.69 ± 0.30Aa 10.00 ± 0.00Aa 18.00 ± 1.00Ad 2.06 ± 0.12Ad 1.53 ± 0.23Ad
OB7 50.88 ±0.47Acd − 6.78 ± 0.59Bbc 17.08 ± 4.23bBc 99.67 ± 0.26Aa 7.00 ± 1.00Ab 38.00 ±1.00Ae 4.90 ± 0.10Ac 3.71 ± 0.38Ac
OB10 56.01 ± 0.23Ac −7.97 ± 0.03Bab 23.02 ± 0.30Bab 99.62 ± 0.26Aa 6.00 ± 0.00Ab 44.00 ± 1.00Af 7.14 ± 0.12Ab 5.56 ± 0.33Ab
OS3 48.70 ± 0.18Ad −5.96 ± 0.13Bab 22.65 ± 0.26Aab 99.62 ± 0.36Aa 5.00 ± 0.00Bbc 53.00 ± 1.00Ba 2.20 ± 0.03Ad 2.21 ± 0.01Ad
OS7 60.17 ± 0.64Ab −7.23 ± 0.32Ba 28.72 ± 0.39Aa 99.57 ± 0.29Aa 3.50 ± 0.50Bc 86.00 ± 2.00Bb 4.84 ± 0.04Ac 4.92 ± 0.04Abc
OS10 65.78 ± 0.08Ab −7.76 ± 0.18Ba 29.50 ± 0.12Aa 99.59 ± 0.39Aa 4.00 ± 0.00Bc 104.00 ± 2.00Bc 6.76 ± 0.12Ab 7.17 ± 0.05Aa
BM 85.34 ± 1.21Ba −2.68 ± 0.05Ac 12.17 ± 0.07Bc − − − 7.70 ± 0.01Aa 1.63 ± 0.10Bd
Capital case letters within each column compare the 2 types of organogels (OBs and OSs) and BM sample (P ࣘ 0.001). Lower case letters compare the 7 samples with each other
within each column (P ࣘ 0.001).

Table 2–The DSC measured thermal properties of the BW and SW organogels (Mean±Sd).

Crystallization Melting

E: Food Engineering &

Sample Onsetc (˚C) Peak(Tc) (˚C) Hc (J/g) Onsetm (˚C) Peak(Tm) (˚C) Hm (J/g)

Physical Properties
OO −13.49 ± 0.49Dg −17.19 ± 0.19Eg −6.15 ± 0.15Aa −12.65 ± 1.46De −3.96 ± 0.46Eh 71.36 ± 1.13Cc
BW 60.76 ± 0.03Bb 58.28 ± 0.18Bb −171.29 ± 8.32Bb 51.97 ± 0.38Bb 63.15 ± 0.17Bb 174.44 ± 6.17Bb
SW 74.05 ± 0.13Aa 69.27 ± 0.16Aa −197.40 ± 6.66Cc 68.78 ± 0.14Aa 76.29 ± 0.03Aa 199.68 ± 9.22Aa
BM 37.42 ± 0.01Ef 16.16 ± 0.08Df −2.28 ± 0.14Aa 37.42 ± 0.01Cc 40.36 ± 0.00Dg 76.80 ± 0.21Cc
OB3 38.04 ± 1.40Ce 35.06 ± 0.51Ce −2.40 ± 0.40Aa 30.53 ± 0.43Bd 44.36 ± 0.23Bf 2.64 ± 0.24Dd
OB7 45.97 ± 1.14Cd 41.00 ± 1.59Cd −8.52 ± 0.25Aa 36.62 ± 0.53Bcd 49.18 ± 0.45Be 10.93 ± 0.29Dd
OB10 47.04 ± 0.07Cd 43.79 ± 0.12Cd −12.99 ± 0.92Aa 40.04 ± 1.87Bc 50.08 ± 0.28Be 11.96 ± 0.75Dd
OS3 54.66 ± 0.53Bc 51.53 ± 1.05Bc −6.11 ± 0.25Aa 47.58 ± 1.92Cb 58.26 ± 0.18Cc 7.47 ± 1.27Dd
OS7 59.71 ± 0.25Bb 57.24 ± 0.51Bb −10.74 ± 0.01Aa 51.48 ± 1.04Cb 61.37 ± 0.33Cd 13.27 ± 1.39Dd
OS10 62.72 ± 1.38Bb 58.63 ± 0.05Bb −17.32 ± 0.55Aa 48.01 ± 1.18Cb 63.59 ± 0.48Cb 18.39 ± 0.95Dd
Capital case letters within each column compare the 2 types of organogels (OBs and OSs), olive oil (OO), beeswax (BW), sunflower wax (SW), and BM sample (P ࣘ 0.001). Lower
case letters compare the 10 samples with each other within each column (P ࣘ 0.001).

(particularly at 3% addition level) and that of BM were detected feel, among the other polymorphs (Dassanayake and others 2009).
to be quite close to each other (Table 2). In Figure 1, the XRD patterns of BW and SW organogels under
static conditions at 20 °C are presented. The XRD patterns of BW
Crystal structure and morphology of the OO organogels and SW organogels seemed to be very similar and the main peaks
The XRD patterns of the organogels provide information about were 4.70, 4.10, and 3.70 Å. Similar peaks around 3.70 and 4.10 Å
the crystal morphology (Dassanayake and others 2009). The poly- were observed for Candelilla, Carnauba, and Rice Bran wax gels
morphic structures are the most important ones in table-spreads with OO (Dassanayake and others 2009). According to Chopin-
and related products. Triacylglycerol (TAG) crystal polymorph Doroteo and others (2011), these peaks were related to the β
shows α, β, and β  forms. The β  form is preferred for its dis- form polymorph of TAGs. Interestingly, the results

of organogel
persibility, smooth texture, optimum melting, and good mouth- XRD peaks at 3.75 and 4.14 Å were similar to β form (Figure 1).

Figure 1–The X-ray diffraction patterns of the samples: (A) beeswax, (B) sunflower wax, (C) breakfast margarine, (D) OB7, and (E) OS7.

Vol. 79, Nr. 9, 2014 r Journal of Food Science E1735

 Olive oil organogels . . .
Mean crystal sizes calculated from the XRD patterns data are given
in Table 1. The crystal sizes of the BW organogels ranged from
18.00 to 44.00 Å, and that of the SW organogels were between
53.00 and 104.00 Å. In both types of the organogels, mean crystal
size enhanced as the added level of the waxes increased. In one
study, the crystal sizes of monoglyceride organogels with cod liver
oil have shown to decrease as the applied shear rate increases (Da
Pieve and others 2010).
PLMs provide information about the crystal structures of
the organogels. The PLM pictures of BW and SW organogels
E: Food Engineering &
Physical Properties
Figure 2–The polarized light microphotographs (PLM) of the organogel samples: (A) OB3, (B) OB7, (C) OB10, (D) OS3, (E) OS7, and (F) OS10.
E1736 Journal of Food Science r Vol. 79, Nr. 9, 2014
prepared with different addition levels are shown in Figure 2. The
PLM pictures of the organogel samples under static conditions
and only fresh samples were taken. The SW compared to the BW
was found to have longer fibrous crystals in organogel systems.
These differences might be due to the different types of waxes
used. Similar microphotographs were taken by Dassanayake and
others (2009). Furthermore, these researchers reported that the
fiber-like, smaller needle crystals formed stronger and hard gels.
Additionally, these types of gels have higher OBC, as well as higher
melting and crystallization points (Dassanayake and others 2009).
Figure 3–The textural properties of the
organogel and breakfast margarine
samples during storage: (A) firmness value
of the samples stored at 4 °C, (B) firmness
value of the samples stored at 20 °C, (C)
work of shear values of the samples stored
at 4 °C, (D) work of shear values of the
samples stored at 20 °C, (E) stickiness
values of the samples stored at 4 °C, and
(F) stickiness values of the samples stored
at 20 °C.
Olive oil organogels . . .
Textural and oxidative stability of OO organogels during
storage
To understand the effect of storage time and temperature on
the organogel stability, the textural parameters of the organogel
samples stored at 4 and 20 °C were monitored for 90 d. Textural
parameters such as “firmness” “work of shear” and “stickiness”
values were determined. During the storage period, the mea-
surements were done at the end of each month, and for each
measurement, the organogel samples were used only once. The
firmness value provides information about the hardness of the sam-
ples. The firmness values of the BW organogels varied between
29.10 and 636.41 g at 4 °C, and 19.40 and 605.44 g at 20 °C
during the storage period (Figure 3A and 3B). On the other hand,
the firmness values of the SW organogels were in the range of
155.04 and 924.89 g at 4 °C, and 110.05 and 584.86 g at 20 °C.
As expected, the gels stored at 4 °C were firmer than those stored
at 20 °C (P ࣘ 0.05) (Figure 3A and 3B). The firmness values of
the whole samples significantly varied during the storage period
(P ࣘ 0.001). In addition to these results, it was found out that
SW gels were harder than BW gels (P ࣘ 0.001). Furthermore,
the results revealed that the firmness of the samples depended on
wax concentration (P ࣘ 0.001) (Figure 3A and 3B). As a re-
sult, the organogels containing 10% level of wax were harder than
those with 3% wax addition level. The firmness values of the SW
organogels prepared with sunflower oil were measured by Hwang
and others (2012). Similarly to our findings, Hwang and others
(2012) indicated that as SW concentration increased, the firmness
values also increased. Most importantly, both SW and BW gels
preserved their textural stabilities at each storage conditions. The
firmness values of the BM samples ranged from 72.31 to 102.90
at 20 °C and from 158.97 to 250.51 at 4 °C (Figure 3A and
3B). When the firmness values of the gels were compared with
the control sample (BM), it was found out that OS3 and OB7
Figure 4–The peroxide values of the organogel samples stored at (A) 4 and 20 °C, at the end of the storage period. These results have revealed
(B) 20 °C.
organogels exhibited similar results, while the other organogel
samples were different (P ࣘ 0.001). Hwang and others (2012)
suggested that sunflower organogels developed with addition level
from 1% to 6% SW may replace hydrogenated fats. The other
analyzed textural parameter of both gels was “work of shear.” The
measurements of “firmness” and “work of shear” provide informa-
tion about organogel spreadability. These parameters are generally
highly correlated. Spreadability is explained as deformation under
an external load (Moskowitz 1987). The “work of shear” values
of BW samples ranged from 20.70 to 1752.04 gs, while those of
SW organogels ranged from 187.68 to 2119.24 gs (Figure 3C and
3D). The “work of shear” values of all samples were significantly
affected by the storage time and temperature (P ࣘ 0.001). Clearly,
the results indicated that BW and SW organogels with same addi-
tion levels exhibit similar “work of shear” values and spreadability
E: Food Engineering &
at both storage temperatures (P ࣘ 0.001) (Figure 3C and 3D). In
Physical Properties
a previous study, it was reported that “work of shear” values of
the organogels prepared with 3% candelilla wax and safflower oil
ranged from 2415.46 to 2742.98 g/mm at 5 °C and from 1455.54
to 1542.15 g/mm at 25 °C (Toro-Vazquez and others 2007). These
findings differ from our results. The differences between the results
might be due to the different types of waxes used as well as the
analytical methods applied. When the “work of shear” values of
the gels were compared with the BM sample, it became clear that
OS3, OB3 organogels, and BM exhibit similar results, while the
other organogel samples were significantly different from BM (P
ࣘ 0.001). The stickiness of the organogels was also measured (Fig-
ure 3E and 3F). Moskowitz (1987) reported that “spreadability”
was related with the firmness and stickiness values of the products.
Not only, the stickiness values of the organogels were affected
by storage temperature and time (P = 0.05), but also, they were
affected by wax types and addition levels (P ࣘ 0.05) (Figure 3E
and 3F). As a result, SW organogels were less sticky than BW
organogels (Figure 3E and 3F). On the other hand, the stickiness
values of the BM samples on average were 90 g at 4 °C and 45 g
at 20 °C. According to Figure 3(E) and 3(F), the stickiness values
of the OS3 and BM were quite similar. However, the stickiness
values of OB3 were lower than BM, while that of OB7, OB10,
OS7, and OS10 were higher.
PV is one of the best parameters for the evaluation of oxidation
during storage. In order to determine the effect of storage time
and temperature on the oxidative stability of the organogels, the
measurement of PVs of the samples stored at 4 and 20 °C has been
monitored for 90 d. Figure 4(A) and 4(B) present the determina-
tion of PVs of BW and SW organogels. BM was used as control
sample. Although, the PVs of BM were found to increase at 60th
and 90th d at both storage temperatures, 4 and 20 °C, there were
no major changes in the PVs of the organogels during storage. This
might quite be due to the natural antioxidants present in the OO.
Furthermore, organogels are anhydrous systems, while margarine
includes water, and this situation may cause the difference in the
oxidative stability during storage. The PVs of the gels were affected
by storage temperature (P ࣘ 0.001); however, they were not af-
fected by wax types and addition levels (P = 0.442). At the end
of the storage period, the PVs of OB3 gel were 1.66 at 20 °C and
1.61 at 4 °C. Similar findings have been found for SW gels. Ac-
cording to Codex Alimentarious (2001) (Codex Stan 33-1981),
the maximum allowed PV for OO is 20.00 meqO2 /kg. With
reference to Codex Alimentarious, the PVs of the organogels were
within legal limits (Codex Stan 33 to 1981). On the other hand,
the PVs of the control sample (BM) were 0.54 at 4 °C and 2.71 at
Vol. 79, Nr. 9, 2014 r Journal of Food Science E1737
 Olive oil organogels . . .
that storage temperature significantly affected PV. Rudzinska and
others (2014) reported that the PV values of margarine enriched
with phytosterols/phytostanols were 9.40 at 4 °C and 35.40 at
20 °C after 90 d of storage. In our study, PVs of the organogels
were lower than that of the BM sample at the end of the stor-
age at 20 °C. Hence, it can be concluded that both organogel
types may be valuable for replacing hydrogenated fats or table-
spreads.
Conclusion
In this research, OO organogels containing BW and SW were
prepared and their characteristics were compared with each other
and breakfast margarine. Plastic fats are traditionally manufactured
by hydrogenation, partial hydrogenation, fractionation, and inter-
E: Food Engineering &
esterification with time-consuming and expensive technologies.
Physical Properties
Also, these techniques have some disadvantages such as trans-fatty
acids and saturated fat formation. Therefore, these products may
lead to obesity and cardiovascular diseases. Compared with the
existing technologies, organogelation was more rapid, healthier,
and cheaper in respect of technique. This study indicates that
organogels may be used in the replacement of plastic fats. The SFC
of organogels depending on the wax concentrations increased.
SFC values of the organogels were lower than that of BM. Ac-
cording to the PLM images, all samples have needle-like crystals.
XRD patterns of the gels were quite similar among each other
and structurally were similar to β  form. Organogels exhibited
thermoreversible gelation and maintained their textural stabilities
up to 3 mo at both room and refrigerator conditions. Particularly,
the thermal properties of OB3 gel and textural properties of OS3
and OB7 gels were closely similar to breakfast margarine. During
the storage period, the oxidative stability of the organogels was
better than that of BM sample at 20 °C.
As a result, BW gels with an addition level of 7% or less and
SW gels with an addition level of 3% or less organogels may be
used for manufacturing products similar to spreadable margarine.
Furthermore, the other organogels can be considered as replacers
for shortenings and kitchen margarines.
Acknowledgments
This research is funded by the Scientific and Technical Council
(TÜBİTAK) of Turkey as the COST 112O038 project within
COST FA 1001 Action. The authors gratefully thank for the
funding.
E1738 Journal of Food Science r Vol. 79, Nr. 9, 2014
Conflict of Interest
No conflict of interest was reported and the authors were re-
sponsible for the content of this article.
Author Contributions
E. Yılmaz designed the study and interpreted the results. M.
Öğütcü collected test data and analyzed the data statistically.
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