Food Research International 72 (2015) 37–46

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Food Research International

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Monoglyceride organogels developed in vegetable oil with and

without ethylcellulose
A. Lopez-Martínez a, M.A. Charó-Alonso a, A.G. Marangoni b, J.F. Toro-Vazquez a,⁎
a
Facultad de Ciencias Químicas, Centro de Investigación y Estudios de Posgrado, Universidad Autónoma de San Luis Potosí, Mexico
b
Department of Food Science, University of Guelph, Guelph, Ontario, Canada

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

Article history: We used two commercial monoglycerides (MGs) with different composition (SKB, ≈79% glycerol monostearate
Received 7 January 2015 and ≈12% glycerol monopalmitate; PKB, ≈47% glycerol monostearate and 47% glycerol monopalmitate) to develop
Received in revised form 3 March 2015 organogels [2% and 8% (wt/wt) MG content]. The objective was to investigate the effect of shearing (SH) and the
Accepted 11 March 2015
presence of 6% ethylcellulose (EC) as factors to limit the sub-α to β polymorphic transition of MG, and the
Available online 18 March 2015
subsequent crystals agglomeration that results in deleterious effect on the organogel's mechanical and oil-binding
Keywords:
properties. The results showed that under static conditions (ST) both type of MG developed organogels (OG), but
Organogels their structure, measured as the complex modulus (G*), was weak particularly in the organogels formulated with
Monoglycerides PKB at 2%. Nevertheless, the OG-ST had higher strength and lower oil loss than the OG-SH. The X-ray analysis
Crystallization showed that the use of shear during organogelation reduced the time at which the sub-α to β polymorphic
Oil loss transition occurred in both the SKB and the PKB oleogels. Additionally, shearing seemed to hinder the formation
Rheology of well-organized microplatelet structure, and from there the lack of gelation in the 2% OG-SH and the higher oil
loss of the 8% OG-SH compared with their static counterparts. Independent of the concentration of SKB and PKB,
the presence of EC resulted in organogels with higher G* than that for OG-ST without EC. This, in spite the EC con-
centration used was below the critical concentration for vegetable oil gelation. The results showed that EC slowed
the rate for the sub-α to β polymorphic transition in the MG organogels. Thus, irrespective of the type of MG and
the concentration used, during 14 days of storage at 15 °C the OG-EC systems showed a lower oil loss as a function
of time than the corresponding organogels developed without EC. This was particularly evident in the organogels
formulated with SKB and those formulated with 8% of MG. We suggest that EC limits the molecular mobility in
the MG organogels, and therefore, slows the sub-α to β polymorphic transition and the subsequent β crystals' ag-
glomeration. The results showed that there is a synergistic interaction between MG and EC that result in organogels
with higher viscoelastic properties and lower oil loss than those observed in MG-organogels without EC.
© 2015 Elsevier Ltd. All rights reserved.

1. Introduction Monoglycerides (MGs) form organogels in vegetable oils through the

Molecular organogels are systems with useful physicochemical and
functional properties for the development of trans-free edible spreads
without the use of saturated fats, pharmaceutical and cosmetic products
with controlled release of bio-active molecules, and also products with
application in catalysis, oil recovery, and information recording
(Basak, Nanda, & Banerjee, 2012; Hughes, Marangoni, Wright, Rogers,
& Rush, 2009; Sagiri et al., 2014; Sangeethaa & Maitra, 2005;
Toro-Vazquez et al., 2007). Molecular organogels are bicontinuous,
frequently colloidal systems structured as aggregated low molecular
mass organic molecules and an organic liquid trapped within, including
vegetable oils.
⁎ Corresponding author at: Facultad de Ciencias Químicas-CIEP, Av. Dr. Manuel Nava 6,
Zona Universitaria, San Luis Potosí, SLP 78210, Mexico. Tel.: +52 444 8262460.
E-mail address: toro@uaslp.mx (J.F. Toro-Vazquez).
formation of inverse lamellar phases (Chen & Terentjev, 2009, 2011; Da
Pieve, Calligaris, Co, Nicoli, & Marangoni, 2010; López-Martínez et al.,
2014; Ojijo et al., 2004; Ojijo, Neeman, Eger, & Shimoni, 2004). Thus, in
the hydrophobic environment (i.e., vegetable oil) the hydrophilic head
groups of the MGs are now in the middle of the bilayer adopting a two-
dimensional close-packed conformation (i.e., 2D hexagonal lattice)
(Chen, Damme, & Terentjev, 2009). This organization is stabilized by
the hydrogen bonds between the secondary and primary −OH groups
of the MGs throughout the bilayers. Eventually, this hydrogen bonding
pattern leads to the crystallization of the aliphatic tails in the MGs devel-
oping more stable polymorphs (i.e., sub-α and, eventually, the β phase).
Additionally, this glycerol head self-assembly is responsible for the for-
mation of the inverse lamellar phase that leads to oil gelation and pro-
vides elastic properties to MGs-oil system. This rheological behavior has
mechanical properties that could be used in the production of trans-free
substitutes for butter and lipid spreads (López-Martínez et al., 2014). Un-
fortunately, the sub-α to β polymorphic transition and the β crystals'

http://dx.doi.org/10.1016/j.foodres.2015.03.019
0963-9969/© 2015 Elsevier Ltd. All rights reserved.
38 A. Lopez-Martínez et al. / Food Research International 72 (2015) 37–46
agglomeration that occurs as a function of time, result in a significant
modification of the three-dimensional crystal network with the subse-
quent deleterious effect in the thermal, mechanical and oil-binding prop-
erties of the organogel (Chen & Terentjev, 2009).
Within this context, we studied the effect of shear and the addition
of a polymer gelator on the structure and properties of MG organogels.
The main aim of the investigation was to limit the polymorphic and mi-
crostructural changes that occur during storage of MG organogels to in-
crease their utility, particularly their oil binding capacity.
Da Pieve et al. (2010) studied the effects of shear on the microstruc-
ture and oil binding capacity of 5% MG organogels in cod liver oil. These
authors observed that shearing during crystallization resulted in the for-
mation of weak gels structured by small crystal clusters with low oil
binding capacity (Da Pieve et al., 2010). However, Alvarez-Mitre,
Morales-Rueda, Dibildox-Alvarado, Charó-Alonso, and Toro-Vazquez
(2012) showed that candelilla wax organogels developed by applying
shear in the metastable region prior to crystallization had a higher
storage modulus and less oil loss than organogels prepared under static
conditions. These results suggest that the use of shear under specific
time-temperature conditions can yield MG-organogels with improved
microstructural and oil-binding properties than organogels developed
under static conditions.
On the other hand, the use of polymeric gelators has recently emerged
as a strategy to structure vegetable oils without the use of trans-fats or
saturated fats. However, there is only one polymer that is known to gel
oils, ethylcellulose (EC), a linear polymer of 1,4-β-D-glucose units with
ethyoxy substitutions at carbons 2, 3, or 6 (Dey, Kim, & Marangoni,
2011; Laredo, Barbut, & Marangoni, 2011; Zetzl, Marangoni, & Barbut,
2012). Zetzl et al. (2012) showed that the organogel strength increased
as the molecular weight and the concentration of EC increased. In EC
organogels, amphipathic molecules such as MGs, act as plasticizers by
hydrogen-bonding with the unsubstituted hydroxyl groups on the poly-
mer strands (Dey et al., 2011). Through this process, the amphipathic
molecule becomes embedded between polymer strands, limiting the for-
mation of junction zones between polymer strands, increasing the free
volume of the system and thus modifying the viscoelastic properties of
the oleogel. Within this framework, the crystallization of MGs in the
presence of EC at a concentration below the minimum required for EC
gel formation might result in the development of MG organogels with
improved viscoelastic and oil-binding properties than those developed
without EC. Additionally, given the higher viscosity of the oil phase
with EC, we might expect MG organogels with EC added to be more sta-
ble than MG organogels without EC addition.
The objective of this investigation was to evaluate and compare the
oil binding properties of MG organogels with and without EC addition,
formed under static conditions. To understand the differences in the
oil binding capacities of the organogels, we followed the polymorphism
of the MG crystals as a function of storage time by calorimetry and pow-
der X-ray diffraction of the organogels. For comparison purposes, we in-
cluded in the study organogels formulated just with MGs formed under
shear.
2. Materials and methods
2.1. Materials
Canola oil was obtained from a local manufacturer (Bunge Canada, To-
ronto). The Alphadim 90 SKB (SKB) and Alphadim 90 PKB (PKB), both
distilled MGs, were obtained from Caravan Ingredients (Lenexa, KS). Ac-
cording to the gas chromatography analysis, the fatty acid composition
for SKB was 12.0% (wt/wt) (±0.6%) palmitic acid, 78.7% (±6.8%) stearic
acid, and 1.6% (±0.4%) of other fatty acids. The fatty acid composition for
PKB was 46.9% (wt/wt) (±1.9%) palmitic acid, 47.2% (±2.8%) stearic
acid, and 1.2% (±0.2%) of other fatty acids. The technical data sheet for
SKB and PKB indicated a minimum of 90% (wt/wt) of MGs and 1.2%
(wt/wt) maximum of free fatty acids. We assumed that the fatty acid
distribution corresponded to ≈79% (wt/wt) glycerol monostearate (i.e.,
glycerol 1-monostearate) and ≈12% glycerol monopalmitate (i.e., glycer-
ol 1-monopalmitate) for SKB, and ≈47% (wt/wt) glycerol monostearate
and 47% glycerol monopalmitate for PKB. The SKB and PKB were stored
under desiccant conditions at room temperature. To modify the viscosity
of the vegetable oil we used Ethocel standard 4 (Dow Chemical Company,
Midland, MI), an ethylcellulose polymer with 48%–49.5% (wt/wt) ethoxyl
content. According to the manufacturer a 5% (wt/vol) solution of Ethocel
in 80% toluene and 20% ethanol provides a viscosity at 25 °C between
3 mPa·s and 5.5 mPa·s.
2.2. Treatment conditions and calorimetry measurements
2% (wt/wt) and 8% (wt/wt) SKB and PKB organogels (OG) were pre-
pared following three different treatment conditions: static conditions
(ST), shear (SH), and under static conditions in the presence of EC. For
the organogels developed under ST conditions (OG-ST), 2% and 8% SKB
and PKB solutions in canola oil were prepared. Samples (≈5–7 mg) of
the solutions were added to aluminum pans and placed in an oven at
80 °C. After 20 min at this temperature, the pans with the MG solutions
were transferred to a refrigerated chamber and cooled until achieving
15 °C. The approximate cooling rate was 8 °C/min. For the organogels
set under shear (OG-SH), the SKB and PKB solutions (≈20 mL) in
50 mL baker glasses were heated for 20 min at 80 °C in an oven. Then,
the solutions were allowed to cool until achieving 40 °C and then stirred
at 100 rpm for 1 min using an overhead mechanical stirrer (Lightnin
LabMaster, model L1U10F, Wytheville, VA) and a long-shafted stir bar.
After stirring samples (≈5–7 mg) of the solutions were added to alumi-
num pans pre-heated at 40 °C, and immediately transfer to the refrigerat-
ed chamber until achieving 15 °C (≈8 °C/min). For the SKB and PKB
organogels developed under static conditions in the presence of EC
(OG-EC), initially we prepared a 6% (wt/vol) solution of Ethocel standard
4 cP in the vegetable oil. Thus, the corresponding amount of Ethocel stan-
dard 4 cP was added to the vegetable oil while stirring and heating until
achieving 160 °C (i.e., above the glass transition temperature of Ethocel
standard 4 cP). The Ethocel solubilized in the vegetable oil after approxi-
mately 30 min at 160 °C. The glass transition temperature of EC depends
on the average molecular weight of the polymers, and for the Ethocel
standard 4 cP occurs in the interval between 135 and 145 °C (Dow
Cellulosics, 2005). The solutions were allowed to cool to 80 °C, and then
the corresponding amount of SKB or PKB was added with gentle stirring.
Samples (≈5–7 mg) of the solutions were added to aluminum pans pre-
heated at 80 °C and then placed in an oven at 80 °C. After 20 min at this
temperature, the pans were transferred to the refrigerated chamber
until reaching 15 °C (≈8 °C/min). After predetermined storage times be-
tween 0 and 14 days, the pans with the OG-ST, OG-SH, and OG-EC were
sealed and heated from 15 °C to 80 °C at 5 °C/min in a differential scanning
calorimeter (Model Q2000, TA Instruments; New Castle, DL). The temper-
ature at the maximum heat flow (Tm) of the melting endotherm and the
corresponding heat of melting (ΔHm) were calculated with the
instrument's software as described previously (Toro-Vazquez, Morales-
Rueda, Mallia, & Weiss, 2010).
2.3. X-ray diffraction
The treatment conditions to develop the OG-ST, OG-AG, and OG-EC
were the same as those described in Section 2.2. However, for the X-ray
diffraction measurements, the organogels were set (15 °C) in rectangu-
lar glass cells of 1 × 1 × 0.5 cm. The small and wide-angle X-ray
diffractograms (SAXS and WAXS, respectively) of the organogels were
obtained at predetermined days between 0 days and 14 days of storage
at 15 °C. For the WAXS measurements, the scanning was performed
from 16° to 30° at a rate of 0.03 °/min and for the SAXS measurements,
from 0.9° and 8° at a rate of 1 °/min. Data processing and analyses were
performed using Jade 6.5 (MDI Corporation, City, State). The X-ray
diffractometer (Multiflex, Rigakug, Japan) was equipped with
 A. Lopez-Martínez et al. / Food Research International 72 (2015) 37–46 39

temperature controlled sample holder and a lamp producing CuKα X- 3. Results

rays (λ = 1.54 Å) at 44 kV and 44 mA, with collimator slits set at
0.3 mm. Previously, we reported the phase diagrams and rheological behavior
of organogels developed by pure glycerol monostearate (93.5% pure) and
a commercial MG (37% glycerol monostearate and 54% glycerol
2.4. Organogel oil binding capacity
monopalmitate) in high oleic sunflower oil (López-Martínez et al.,
2014). Since the compositions of these pure and commercial MGs are
The oil binding capacity of the organogels as a function of storage
similar to SKB and PKB, respectively, some results obtained in the present
time at 15 °C, was determined measuring the percentage of oil loss fol-
investigation will be compared to those previously published. Based on
lowing a slight modification of the methodology described by Dibildox-
these results, the storage temperature of 15 °C used in the present
Alvarado, Neves, Gioielli, Toro-Vazquez, and Marangoni (2004). The
investigation assured that the glycerol monostearate and glycerol
treatment conditions to develop the OG-ST, OG-AG, and OG-EC were
monopalmitate present in the SKG and the PKB structured the organogels
the same as those described in Section 2.2. However, in this case the
mainly in the sub-α and the inverse lamellar phase (Lα) phase, respec-
gels were set (15 °C) in aluminum cylindrical molds (10-mm diameter
tively. On the other hand, at 40 °C, the temperature at which shear was
and 6-mm thickness) equipped with a circulating liquid jacket connect-
applied to develop the SH organogels (see Section 2.2), the SKB system
ed to a programmable water bath (Julabo F32-MW; Seelbach,
was in the sub-α1 phase while the PKB system was in the Lα phase.
Germany). Once the samples appeared solid were removed from the
molds and deposited onto a stack of pre-weighted filter papers
3.1. SKB and PKB organogels set under static conditions
(Whatman #5, 125-mm diameter). The weight of the filter papers
(wtp) and of the organogel on the filter papers (wtp + og) were recorded.
Fig. 1 shows the melting thermograms for the 2% and 8% SKB (Fig. 1A)
Afterwards, we stored the organogels on the filter papers at 15 °C and,
and PKB (Fig. 1B) organogels prepared under static conditions. In
after predetermined storing times between 0 and 14 days, the gel was
previous investigations, the melting behavior of OG-ST with 1.5% to 8%
carefully removed and the filter papers weighted (wtp + oil). For each
(wt/wt) glycerol monostearate (93.5% pure) in high oleic safflower oil
type of organogel investigated four independent determinations were
showed the presence of three endotherms associated with the sub-α2,
done. The percentage of oil lost by the organogels to filter papers was
sub-α1, and Lα crystal states (López-Martínez et al., 2014). In contrast,
determined using the Eq. (1):
in the present study the melting behavior of the 2% and 8% SKB
organogels showed just two endotherms. The lower melting temperature
    endotherm was associated with the sub-α ↔ Lα transition, and the
%ðwt=wtÞoil loss ¼ wtpþoil −wtp = wtpþog −wtp  100: ð1Þ

2.5. Polarized light microscopy

The treatment conditions to develop the OG-ST, OG-SH, and OG-EC

were the same as those described in Section 2.2. However, here the
SKB and PKB solutions were crystallized on a microscope slide at
15 °C. The slides were stored at 15 °C obtaining polarized light micro-
photographs (PLM) as a function of time using a Leica DM RXA2 micro-
scope (Leica Microsystems, Richmond Hill, Canada) equipped with a
color video camera (QImaging, Retiga 1300i Fast 1394 Burnaby BC,
Canada) and a heating/cooling stage Linkam LTS350 (Linkam Scientific
Instruments Inc., Surrey, England) connected to a LTS 350 temperature
control station (Linkam Scientific Instruments, Ltd.) and a liquid nitro-
gen tank.

2.6. Rheology measurements

The complex modulus (G*) of the canola oil, the canola oil with 6%
EC, the 2% and 8% SKB and PKB organogels developed under static con-
ditions with and without EC were measured in a small deformation os-
cillatory rheometer (Paar Physica MCR 301, Stuttgart, Germany) using a
steel truncated cone-plate geometry (CP25-1/TG), equipped with a
true-gap system. The sample temperature was controlled through a
Peltier temperature control located on the base of the geometry and
with a Peltier-controlled hood (H-PTD 200). The control of the equip-
ment was made through the software Start Rheoplus US200/32 version
2.65 (Anton Paar, Graz, Austria). Organogel melts at 80 °C were applied
to the base of the geometry (80 °C), and the cone gap was set using the
true-gap function of the software. After 30 min at 80 °C, the system was
cooled at 8 °C/min until achieving 15 °C. At this temperature the G* of
the canola oil, the canola oil with 6% EC, the OG-ST, and OG-EC were
measured as a function of time using a strain between 0.01% and 0.1%
and a frequency between 1 and 10 Hz, always within the linear visco- Fig. 1. Melting thermograms for the 2% and 8% (wt/wt) SKB (A) and PKB (B) organogels
elastic region of the system. developed under static conditions after 0 days of storage at 15 °C.
40 A. Lopez-Martínez et al. / Food Research International 72 (2015) 37–46
second endotherm with the melting of the Lα phase (Fig. 1A). Chen and
Terentjev (2009) observed similar melting behavior in fresh (0 days of
storage) organogels developed at 26 °C by 10% (wt/wt) of a commercial
MG (≈93% glycerol monostearate and ≈7% glycerol monopalmitate)
in hazelnut oil. These authors associate the first endotherm to the melting
of the crystallized carbon chains of sub-α crystals, and the second endo-
therm to the melting of the Lα phase. The SKB organogels did not show
the presence of a sub-α2 phase. The sub-α1 ↔ sub-α2 reversible transi-
tion is particularly sensitive to the presence of impurities (i.e., 2-mono-
stearoyl-glycerol and free fatty acids) (Chupka, Yanowitz, Chiu,
Alleman, & McCormick, 2011; Lutton, 1971; Vereecken et al., 2009). As
previously indicated, although the major component of SKB was glycerol
monostearate (i.e., 79%), it also contained 12% glycerol monopalmitate,
and approximately 1.2% of other components (e.g., 2-monoglycerides,
free fatty acids). These components might impair the development of
the sub-α phase in the SKB organogels.
The corresponding WAXS spectra for the 2% and 8% SKB organogels
(Fig. 2A) showed the presence of an amorphous signal with scattering
that peaked at 4.55 Å. This diffraction behavior is clearly associated
with the presence of a liquid phase of triacylglycerols from the vegeta-
ble oil (Larsson, 1972). In spite of the amorphous phase of liquid triacyl-
glycerols and independent of the SKB concentration in the organogel,
the WAXS spectra showed a major sharp peak at 4.21 Å (± 0.00 Å),
and a sequence of small diffraction peaks at d values of 3.65 Å
(±0.01 Å), 3.80 Å (±0.01 Å), 3.95 Å (±0.01 Å), and 4.34 Å (±0.01 Å)
(Fig. 2A). In the same way the SAXS spectra showed a sharp peak at
49.58 Å (± 1.10 Å) (data not shown). All these diffraction peaks are
characteristic of the sub-α phase.
Fig. 2. WAXS spectra for the 2% and 8% (wt/wt) SKB (A) and PKB (B) organogels developed
under static conditions after 0 days of storage at 15 °C.
In contrast to the SKB organogels, the melting thermograms of the 2%
and 8% PKB organogels developed under static conditions showed just
one endotherm with a Tm of 38.5 °C (±0.5 °C) and 52.7 °C (±0.0 °C), re-
spectively (Fig. 1B). Based on previous results (López-Martínez et al.,
2014), a commercial MG with similar composition (i.e., 37.7% glycerol
monostearate and 54.0% of glycerol monopalmitate) to PKB showed
that above 15 °C just a mixed Lα phase exists. The stearic and palmitic
acid have similar molecular structures and thus the glycerol monostearate
and glycerol monopalmitate present in PKB could co-crystallize during
cooling developing a mixed Lα structure as previously shown by López-
Martínez et al. (2014). Therefore, the endotherm observed in the PKB
organogels (Fig. 1B) was associated with the mixed Lα phase ➝ isotropic
phase transition. Chen et al. (2009) showed that the Lα phase of pure
glycerol monostearate (i.e., 92% glycerol monostearate and 5% glycerol
monopalmitate) displayed a small-angle reflection at 52 Å, corresponding
to the thickness of the lamellar bilayer, and wide-angle reflections at
4.17 Å and 4.11 Å corresponding to the closest distance of approach of
glycerol heads in a plane and the distance between neighboring glycerol
heads in different layers, respectively. The SAXS spectra for the 2% and
8% PKB organogels developed under static conditions showed a sharp
peak with a d value of 49.23 Å (±0.49 Å) (data not shown); however,
just the 8% PKB organogels showed a single short space diffraction peak
at 4.23 Å (±0.01 Å) (Fig. 2B). These structural features differ somehow
from the values characteristic of the Lα phase for pure glycerol
monostearate. However, as previously discussed, in the PKB organogels
the Lα structure is formed by glycerol monostearate and glycerol
monopalmitate. Therefore, the structural characteristics of this mixed
Lα structure might slightly differ from those present in the Lα phased de-
veloped just by glycerol monostearate. Additionally, the amorphous re-
gion associated with the liquid phase of triacylglycerols from the
vegetable oil could overshadow the 4.11 Å diffraction peak corresponding
to the Lα phase (Fig. 2B).
3.2. Changes during storage of SKB and PKB organogels developed under
static conditions
The changes occurring in the OG-ST as a function of storage time at
15 °C were evaluated by DSC (Fig. 3) and WAXS diffraction (Fig. 4). As
previously discussed, the melting behavior of the 2% and 8% SKB
organogels at 0 days of storage at 15 °C showed the endotherms associ-
ated to the sub-α ↔ Lα transition and melting of the Lα state (Fig. 1A,
Fig. 3A and B). However, after two days of storage, the 2% SKB
organogels showed just one endotherm and, as storage time increased,
a new endotherm appeared with a higher Tm (64.9 °C ± 1.2 °C). This en-
dotherm increased in size as a function of storage time (Fig. 3A). The de-
velopment of this new endotherm took place in parallel with a
concomitant decrease in the peak observed at 4.21 Å (±0.00 Å), the ap-
pearance of a strong line at the 4.16 Å (±0.01 Å), at d-spacings of 4.46 Å
(± 0.01 Å) and 4.60 Å (± 0.03 Å), and a better definition of the short
spacings with d of 4.02 Å (± 0.01 Å), 3.92 Å (± 0.02 Å), and 3.84 Å
(±0.01 Å) (Fig. 4A). The β′ polymorph of pure glycerol monostearate
has a strong short spacing at 4.15 Å (Lutton & Jackson, 1948). Thus,
we associated the appearance of these short spacing peaks, the disap-
pearance of the diffraction peak at 4.21 Å and the melting behavior of
the 2% SKB organogels with the sub-α ➝ β′ ➝ β polymorphic transition
(Chen et al., 2009; Krog, 2001) occurring during storage at 15 °C. Ac-
cording to Lutton and Jackson (1948) and Hagemann (1988), the β′
polymorph is only formed through quick crystallization from organic
solvents, and it is hardly observed by thermal analysis. Additionally,
the sub-α and β′ phases are remarkably alike in their diffraction pat-
terns and differences between them are just associated with the higher
Tm of the β′ polymorph (Lutton, 1971). In our systems the vegetable oil
might be acting as organic solvent and thus promoting the sub-
α ➝ β′ ➝ β polymorphic transition. In consequence, the overall result
of the sub-α ➝ β′ ➝ β polymorphic transition was an increase of the
melting point of the 2% SKB organogels from 51.4 °C (± 0.6 °C) at
 A. Lopez-Martínez et al. / Food Research International 72 (2015) 37–46 41

Fig. 3. Melting thermograms for the 2% (A, C) and 8% (wt/wt) (B, D) SKB (A, B) and PKB (C, D) organogels developed under static conditions. The thermograms were obtained after storage
(15 °C) of organogels at particular times.

0 days of storage to 65.3 °C (±0.3 °C) after 14 days of storage. We ob-
served a similar melting behavior during the storage of the 8% SKB
organogels (Fig. 3B). However, in these organogels the endotherm asso-
ciated with the β phase appeared after two days of storage with a Tm of
68.5 °C (±0.6 °C) increasing in size and Tm (i.e., 69.3 °C ± 0.5 °C after
14 days of storage) as a function of storage time at 15 °C. Nevertheless,
the corresponding WAXS spectra did not display the characteristic dif-
fraction peaks for the β polymorph (Fig. 4B). Nevertheless, we observed
that the ratio of ΔHm between the low and high Tm endotherms was, as
a direct function of storage time, 1.3 to 4.3 times larger in the 8% SKB
organogels than in the 2% SKB organogels. These results indicated that
although the β polymorph was present at earlier stages in the 8% SKB
organogels, its proportion with respect to the tentative β′ crystals was
lower than in the 2% SKB organogels. We consider that given the
low proportion of β crystals in the 8% SKB organogels, the large amor-
phous signal of liquid triacylglycerols masked the diffraction peaks

Fig. 4. WAXS spectra for the 2% (A, C) and 8% (wt/wt) (B, D) SKB (A, B) and PKB (C, D) organogels developed under static conditions. The WAXS spectra were obtained after storage (15 °C)
of organogels at particular times.
42 A. Lopez-Martínez et al. / Food Research International 72 (2015) 37–46

characteristic of the β phase (Fig. 4B). As previously indicated, these dif-

fraction peaks (i.e., 4.46 Å and 4.60 Å) were clearly observed in the 2%
SKB organogels (Fig. 4A).
We already discussed that the melting thermograms for the 2% and 8%
PKB organogels developed statically after 0 days of storage at 15 °C
showed just the endotherm associated with the melting of the mixed
Lα phase (Fig. 1B, Fig. 3C and D). However, this endotherm transformed
into one of a higher Tm just after two days of storage (Fig. 3C and D). The
WAXS spectra as a function of storage time for the 8% PKB organogels
showed that after two days of storage, the short space diffraction peak as-
sociated with the mixed Lα phase (i.e., 4.23 Å ± 0.01 Å) disappeared,
while two diffraction peaks with d values of 4.37 Å (±0.01 Å) and
4.47 Å (±0.00 Å), and a major diffraction peak at 4.56 Å (±0.02 Å) ap-
peared (Fig. 4D). These diffraction peaks are characteristic of the β
state, probably developed through a polymorphic transition directly
from the Lα phase as has been previously suggested by Chen and
Terentjev (2009) and López-Martínez et al. (2014). The 2% PKB
organogels showed similar melting behavior than the 8% PKB organogels
(Fig. 3C). However, the corresponding WAX spectra for the 2% PKB
organogels did not show the characteristic diffraction peaks associated
with the β crystals. In the 8% PKB organogels the endotherm associated
with the melting of the β polymorph was sharper, with larger ΔHm
(11.7 J/g ± 0.2 J/g), and a higher Tm (61.5 °C ± 0.4 °C) (Fig. 3D) than
the corresponding values for the endotherm present in the 2% PKB
organogels (ΔHm = 1.2 J/g ± 0.2 J/g; Tm = 57.9 °C ± 1.3 °C) (Fig. 3C).
This showed that the β crystals were present in lower proportion in the
2% PKB organogels than in the 8% PKB organogels. Thus, given the
lower proportion of β crystals developed in the 2% PKB organogels, prob-
ably the amorphous signal associated with the liquid triacylglicerides
overshadowed the diffraction signals of the β phase.
The oil loss as a function of storage time for the OG-ST is shown in
Fig. 5A. Evidently there is a concentration effect associated with the oil
loss, this since independent of the type of MG and storage time, the 8%
OG-ST always observed significant lower oil loss than the 2% OG-ST
(P b 0.01; Fig. 5A). The higher crystal mass present in the 8% OG-ST result-
ed in higher oil retention by the organogel, while in the 2% OG-ST most of
Fig. 5. Percentage of oil loss (wt/wt) as a function of storage time (15 °C) for the 2% and 8%
the oil was released since the beginning of storage (Fig. 5A). In contrast, (wt/wt) SKB and PKB organogels developed under static (A), shearing conditions (SH),
after 2 days of storage of the 8% organogels, just when the β phase became and in the presence of 6% EC (B).
evident in both the 8% SKB and 8% PKB organogels (Fig. 3B and D, respec-
tively), we observed a significant increase in the oil loss (Fig. 5A). In cor-
respondence, the oil loss for the 8% OG-ST showed a quadratic increase as MG composition than the pure and commercial MGs previously investi-
a function of the storage time at 15 °C (Fig. 5A). As previously stated, the gated (López-Martínez et al., 2014), and therefore we assumed similar
results of Chen and Terentjev (2009) had shown that the sub-α to β poly- crystallization behavior in the 8% SKB and 8% PKB organogels. Thus,
morphic transition and the β crystals' agglomeration that occur during after two days of storage the 8% PKB organogels showed a Tm
storage, modify the organogels' microstructure with the subsequent del- (61.5 °C ± 0.4 °C) and oil loss significantly lower than those observed
eterious effect in their thermal, mechanical and oil-binding properties of by the 8% SKB organogels (Tm = 68.6 °C ± 0.5 °C; Fig. 5A) (P b 0.01).
the crystal network. The formation of the β polymorph during storage The PLM results agreed with our previous observations. The PLM of
of the 8% OG-ST (Figs. 3B, D, 4B, and D), and its relation with the oil loss the organogels showed crystallized MGs as birefringent structures
during storage at 15 °C (Fig. 5A) agreed with these results. However, an against a dark background corresponding to the vegetable oil. At the be-
additional effect in the behavior of the oil loss of the 8% OG-ST has to be ginning of the storage, the crystals had needle-like and plate-like shapes,
considered. Thus, after two days of storage the 8% PKB organogels showed similar to those observed by Kesselman and Shimoni (2007) in a com-
lower oil loss than the 8% SKB organogels (P b 0.01; Fig. 5A). The commer- mercial MGs crystallized at 25 °C in olive oil. Independent of the type of
cial MGs are mainly composed by mixtures of glycerol monostearate and MG used and for the same storage time, the 2% OG-ST had a microstruc-
glycerol monopalmitate. As previously stated, cooling of commercial MGs ture formed with relative lower mass of crystals than the 8% OG-ST
vegetable oil solutions results in the formation of organogels structured [Fig. 1SM(A and E) and Fig. 2SM(A and E) provided as online supplemen-
by mixed Lα developed by the glycerol monostearate and the glycerol tary material]. After 2–4 days of storage, the PLM for the SKB organogels
monopalmitate. This mixed Lα structure further crystallize in the sub-α showed the aggregations of crystal and the developing of large crystal
phase and then, through a polymorphic transition, transformed during cluster with spherulite shape and high birefringence. After 14 days of
storage in the β phase. The crystallization of mixed Lα and sub-α struc- storage the spherultic crystals, associated with the development of the
tures required of higher supercooling than the crystallization of similar β polymorph, were dispersed in a continuous oil phase indicating that
structures developed by pure glycerol monostearate in vegetable oil solu- the crystal network was broken with the subsequent separation of the
tions (López-Martínez et al., 2014). Subsequently, the organogels devel- oil phase [Fig. 1SM(A–D) provided as online supplementary material].
oped by the commercial MGs had a lower Tm, but provided higher Similar behavior was observed in the 2% PKB organogels. Nevertheless,
capacity for uptake and retention of vegetable oil than the corresponding the spherulitic crystals were smaller [Fig. 1SM(E–H) provided as online
organogels developed just with the pure glycerol monostearate (López- supplementary material] than in the 2% SKB organogels. In contrast, in
Martínez et al., 2014). As previously discussed, SKB and PKB have similar the 8% PKB organogels the crystal aggregation observed after 2–4 days
 A. Lopez-Martínez et al. / Food Research International 72 (2015) 37–46
of storage was less evident and did not result in the formation of spheru-
lites [Fig. 2SM(E–H) provided as online supplementary material].
3.3. Changes during storage of SKB and PKB organogels developed
under shear
Comparing the melting thermograms and WAXS spectra for OG-ST
(Figs. 3 and 4) to those set under shear (OG-SH), we concluded that
shearing MG oleogels upon setting reduced the time at which the sub-
α to β polymorphic transition occurred in both the SKB (Figs. 6A, B
and 8A) and the PKB (Figs. 6C, D and 8B) organogels. Thus, independent
of storage time, the 2% and 8% SKB organogels showed just the endo-
therm associated with the β polymorph with a Tm of 59.95 °C
(±1.32 °C) and 67.17 °C (±0.63 °C) (Fig. 6A and B), respectively, and
for the 2% and 8% PKB organogels with a Tm of 55.46 °C (± 1.62 °C)
and 62.28 °C (± 0.25 °C) (Fig. 6C and D). Despite the presence of the
high Tm endotherm associated with the β polymorph, independent of
storage time, the WAXS spectra for the 2% OG-SH showed just an amor-
phous signal corresponding to the liquid phase of triacylglycerols from
the vegetable oil (data not shown). Probably, as for the other crystalliza-
tion conditions previously discussed, the X-ray signal associated with
the low amount of β crystals developed was overshadowed by the
amorphous signal corresponding to the liquid triacylglycerols. As addi-
tional information, the 2% OG-SH did not develop a gel structure. On
the other hand, the 8% SKB organogels showed faint peaks at d-
spacings of 3.67 Å (± 0.01 Å), 3.82 Å (± 0.00 Å), 3.98 Å (± 0.01 Å),
and 4.55 Å (±0.01 Å) (Fig. 8A), and the 8% PKB organogels at d values
of 3.79 Å (± 0.01 Å), 3.94 Å (±0.00 Å), 4.40 Å (± 0.01 Å), and 4.55 Å
(±0.01 Å) (Fig. 8A). However, the diffraction peak at 4.21 Å associated
to the sub-α phase was not observed. This diffraction pattern and the
melting thermograms for OG-SH indicated that stirring induced a sub-
α to β polymorphic transition. Thus, the OG-ST treatment showed the
presence of β crystals from the early stages of storage at 15 °C.
The corresponding oil loss as a function of storage time for oleogels
set under shear is shown in Fig. 5B. As previously stated, the 2% OG-SH
systems did not develop a gel structure, and therefore we could not
measure the amount of oil loss. On the other hand, independent of the
Fig. 6. Melting thermograms for the 2% (A, C) and 8% (wt/wt) (B, D) SKB (A, B) and PKB (C, D) organogels developed under shearing conditions. The thermograms were obtained after
storage (15 °C) of organogels at particular times.
43
type of MG and storage time, the amount of oil loss shown by the 8%
OG-SH organogels (Fig. 5B) was higher (P b 0.05) than by the 8% OG-
ST organogels (Fig. 5A). Additionally, we did not observe any significant
differences in the oil loss between the 8% SKB and the 8% PKB
organogels set under shear. According to the results obtained by Da
Pieve et al. (2010) for 5% MG organogels in cod liver oil, the use of
shear during organogel formation affects the nano and microstructure
of the system. These authors found that in comparison with organogels
set under static conditions, the use of shear (50 s−1 to 2000 s−1) during
crystallization resulted in weaker organogels with higher amounts of oil
loss (Da Pieve et al., 2010). Our results are in line with the results re-
ported by Da Pieve et al. (2010). Independent of the type of MG used,
the PLM for the 8% OG-SH systems showed the presence of needle-
like and plate-like crystal that increased in sized and extent of birefrin-
gence as storage time increased. However, in contrast with OG-ST
(Fig. 2SM provided as online supplementary material), the OG-SH did
not show the development of spherulitic crystals (Fig. 3SM provided
as online supplementary material). The application of shear during
organogelation seemed to hinder the formation of well-organized
microplatelet structure, and from there the lack of gelation in the 2%
OG-SH system and the higher oil loss of the 8% OG-SH systems relative
to their static counterparts.
3.4. Changes during storage of SKB and PKB organogels developed in the
presence of EC
In contrast with the results obtained with the OG-SH, the melting
thermograms and WAXS spectra for OG-EC (Figs. 7 and 8) showed
that, independent of the type of MG used, the presence of EC evidently
increased the time at which the sub-α to β polymorphic transition took
place in the organogels (i.e., SKB Figs. 7A, B and 8C; PKB Figs. 7C, D and
8D). The 2% SKB-EC and 2% PKB-EC organogels did not show any de-
fined diffraction peaks by WAXS or SAXS analysis (data not shown).
The PLM results showed that the amount of crystals present was smaller
than in the OG-ST (Figs. 4SM and 5SM provided as online supplementa-
ry material). However, the melting thermograms of the 2% SKB-EC
organogels at 0 days of storage showed one endotherm with a Tm of
44 A. Lopez-Martínez et al. / Food Research International 72 (2015) 37–46

Fig. 7. Melting thermograms for the 2% (A, C) and 8% (wt/wt) (B, D) SKB (A, B) and PKB (C, D) organogels developed in the presence of 6% EC. The thermograms were obtained after storage
(15 °C) of organogels at particular times.

42.76 °C ± 0.34 °C (Fig. 7A), and for the 2% PKB-EC organogels at
36.68 °C ± 0.15 °C (Fig. 7C). After 2 days of storage the Tm of this endo-
therm, associated with the melting of the sub-α phase, increased in
both types of organogels and then remained constant during the
14 days of storage in the 2% SKB-EC organogels (46.94 °C ± 0.65 °C;
Fig. 7A) and up to 7 days of storage in the 2% PKB-EC organogels
(46.67 °C ± 2.75 °C; Fig. 7C). After 7 days the Tm of the 2% PKB-EC
organogels increased up to 58.34 °C (±0.61 °C) showing the develop-
ment of the β polymorph (Fig. 7C). Nevertheless, as previously stated,
the amount of β crystals present ought to be small since the WAXS anal-
ysis for the 2% PKB-EC organogels did not show any defined diffraction
peaks. It is important to point out that, in contrast with the 2% OG-SH
and 2% OG-ST systems, both the 2% SKB-EC and 2% PKB-EC systems
did develop a gel structure that although weak, and independent of

Fig. 8. WAXS spectra for the 8% SKB (A, C) and 8% (wt/wt) PKB (B, D) organogels developed under shearing conditions (A, B) and in the presence of 6% (wt/vol) EC (C, D). The WAXS spectra
were obtained after storage (15 °C) of organogels at particular times.
 A. Lopez-Martínez et al. / Food Research International 72 (2015) 37–46 45

the type of MG used, the gels showed a lower amount of oil loss than the
2% OG-ST, and only slightly higher than the 8% OG-SH (P b 0.01; Fig. 5A
and B).
Regarding the 8% OG-EC systems, the melting thermograms for the
8% SKB-EC organogels showed two endotherms during the 14 days of
storage (Fig. 7B): a lower melting temperature endotherm associated
with the sub-α ↔ Lα transition (Tm of 34.64 °C ± 1.26 °C), and a higher
melting temperature endotherm (Tm of 56.36 °C ± 0.34 °C) correspond-
ing to the Lα state melting. The corresponding WAXS spectra showed an
amorphous signal, with a major sharp peak at 4.23 Å (±0.01 Å) and a
sequence of small diffraction peaks at d values of 3.71 Å (± 0.00 Å),
4.01 Å (± 0.01 Å), and 4.12 Å (± 0.03 Å) (Fig. 8C). In the same way,
the SAXS spectra showed a sharp peak at 49.35 Å (±0.23 Å) (data not
shown). All these diffraction peaks are characteristic of the sub-α
phase. Evidently, the 8% SKB-EC organogels did not show the endo-
therm nor the diffraction peaks associated with the presence of the β
phase, as observed during the storage of the 8% SKB organogels devel-
oped statically (Figs. 3B and 8A) or under shear (Fig. 6B). In contrast,
the melting thermograms for the 8% PKB-EC organogels showed just
one major endotherm with a Tm of 50.80 °C (± 0.35 °C). After 2 days
of storage, this endotherm developed a shoulder that increased in size
and Tm as storage time increased (Fig. 7D). As with the 8% PKB
organogels developed under static conditions (Fig. 3D), the major endo-
therm was associated with the melting of the mixed Lα phase and the
shoulder developed after 2 days of storage with the development of
the β polymorph (Fig. 7D). The corresponding WAXS spectra as a func-
tion of storage time showed a rather amorphous diffraction pattern
with faint peaks at 4.32 Å (±0.01 Å) and 4.62 Å (±0.00 Å) (Fig. 8D).
Thus, 8% PKB-EC organogels did not show clear evidence of the presence
of the β state, as observed during the storage of the 8% PKB-ST
organogels (Figs. 3D and 4D) or under agitation (Fig. 6D). This probably
because the amount of crystals present in the 8% PKB-EC organogels was
too low.
The results of PLM for the OG-EC agreed with the melting thermo-
grams and X-ray results. Thus, independent of the type of MG and its Fig. 9. Complex modulus (G*) as a function of time at 15 °C for the canola oil, the canola oil
concentration, the OG-EC system showed the development of with 6% EC, in comparison with the 2% (Fig. 9A) and 8% (wt/wt) (Fig. 9B) SKB and PKB
spherultic crystals after 2 to 4 days of storage [Figs. 4SM and 5SM(A–B organogels developed ST and in the presence of 6% EC.
and E–F) provided as online supplementary material]. However, in
comparison with the PLM for the OG-ST [Figs. 1SM and 2SM(A–B and
E–F) provided as online supplementary material] the spherulitic crys-
tals were fewer but larger. This behavior was particularly evident for molecular weight and concentration of EC increase. In the same way,
OG-EC formulated with 8% PKB (Fig. 5SM provided as online supple- these authors showed that the minimum concentration to develop a
mentary material). It is known that amphipathic molecules such as gel depends on the fatty acid composition of the vegetable oil (Zetzl
MGs, act as plasticizers of polymer molecules by hydrogen-bonding et al., 2012). The results obtained in the current investigation showed
the polymer strands through their hydrophilic “head” (i.e., −OH groups that, although the EC concentration used was below the critical concen-
of MGs) (Dey et al., 2011). Within this framework, the MG-EC interac- tration for gelation (i.e., 6%), the G* of the canola oil increased signifi-
tion decreased the effective concentration of MG in the system. There- cantly (P b 0.001). In contrast, both types of MG organogels in canola
fore, independent of the type of MG, the effective MG concentration oil did develop gels in the presence of EC. However, the gel structure
available for crystallization was lower in the systems with EC. Conse- of the 2% MG-EC, measured as G*, was weak particularly in the
quently, for the same crystallization temperature (i.e., 15 °C) and organogels formulated with PKB at 2% (Fig. 9A and B). In correspon-
cooling rate (i.e., 8 °C/min) the supercooling for MG crystallization dence, as previously discussed, independent of the type of MG most of
was lower in the systems with EC than in the systems without EC. As the oil was released from the 2% OG-ST since the beginning of storage
shown by Marangoni (2005), at low supercooling the activation energy while the 8% OG-ST showed a quadratic increase in the oil loss as a func-
for nucleation is harder to overcome leading to greater ease of crystal tion of storage time (Fig. 5A). Within this context, independent of the
growth than nucleation. In contrast, at higher supercooling, the activa- concentration of SKB and PKB, the presence of EC resulted in organogels
tion energy for nucleation is easier to overcome and nucleation is fa- with higher G* (i.e., stronger gels) than that for PKB and SKB organogels
vored over crystal growth that leads to a high nucleation rate and (Fig. 9). These results showed that, regardless the plasticizing effect of
smaller crystals (Marangoni, 2005). The overall result is that in the pres- MGs (Dey et al., 2011), the interaction EC-MG and the crystallization
ence of EC, the “free” MGs crystallized at a lower nucleation rate and the of the “free” (i.e., not bound to EC) MGs resulted in stronger organogels
crystals grew at a higher rate (i.e., crystal growth was favored over crys- in which the sub-α to β polymorphic transition occurred at a slower
tal nucleation) than in the systems without EC. rate than in the OG-ST without EC. MGs can form organogels in vegeta-
To better understand the effect of EC on the MG organogels, we mea- ble oils with desirable viscoelastic properties (López-Martínez et al.,
sured the G* at 15 °C in the canola oil, the canola oil with 6% EC, and the 2014; Ojijo, Kesselman, et al., 2004; Ojijo, Neemanet, et al., 2004). How-
2% (Fig. 9A) and 8% (Fig. 9B) SKB and PKB organogels developed under ever, during storage the MG organogels suffer syneresis resulting from
static conditions with and without EC (Fig. 9). As previously reported by the sub-α to β polymorphic transition and the β crystals' agglomeration
Zetzl et al. (2012) the strength of EC organogels increases as the that take place during storage. As previously stated, these structural
46 A. Lopez-Martínez et al. / Food Research International 72 (2015) 37–46
transitions result in the formation of solid crystal clusters, the subse-
quent breakage of the three-dimensional crystal network and separa-
tion of the oil phase from the MG crystals with concomitant negative
effects on the organogel's mechanical and oil-binding properties
(Chen & Terentjev, 2009; Ojijo, Kesselman, et al., 2004; Ojijo,
Neemanet, al., 2004). The use of EC resulted in a significant increase in
the vegetable oil G* (Fig. 9) limiting the molecular mobility, and there-
fore, slowing the sub-α to β polymorphic transition and the subsequent
β crystals' agglomeration. Consequently, irrespective of the type of MG
and the concentration used, the OG-EC systems showed a significantly
lower oil loss as a function of time than the corresponding organogels
developed without EC (P b 0.05; Fig. 5). These observations were partic-
ularly evident with the organogels formulated with SKB and the
organogels formulated with 8% of MG (Fig. 9A and B).
4. Conclusions
The objective of this investigation was to investigate the polymor-
phism and oil binding properties that occur in MG organogels devel-
oped under static conditions with and without EC addition, and MG
organogels formed under shear. Under static conditions and at both
MG concentrations investigated, the commercial MGs developed weak
organogels and significant oil loss during storage at 15 °C. Nevertheless,
the OG-ST had higher rigidity and lower oil loss than the OG-SH. It was
evident that shear applied during organogelation reduced the time at
which the sub-α to β polymorphic transition occurred in both the SKB
and the PKB organogels. Additionally, shearing hinder the formation of
well-organized structure of MG microplatelets. These two phenome-
nons resulted in the lack of gelation in the 2% OG-SH and the higher
oil loss of the 8% OG-SH, this in comparison with OG-ST.
On the other hand, the results obtained showed conclusively that the
addition of 6% EC (i.e., below the critical EC concentration that produce
oil gelation) to the MG-canola oil systems, resulted in organogels with
higher G* and lower oil lost during storage than that observed by the
OG-ST without EC. Although currently we do not have a particular struc-
tural model for the MG-EC organogels, evidently there is a synergistic
interaction between these components. This MG-EC interaction results
in MG organogels with higher viscoelastic properties and longer stabil-
ity than those observed in MG-organogels without EC. The study of the
factors that determine the MG-EC interaction (i.e., molecular weight of
EC, type and concentration of MGs) might result in the design of new
gel-like formulations with useful physical and functional properties.
Acknowledgments
The investigation was supported by grant # CB-2012-01/177335
from CONACYT. The technical support from Concepcion Maza-Moheno
and Elizabeth Garcia-Leos is greatly appreciated.
Appendix A. Supplementary data
Supplementary data to this article can be found online at http://dx.
doi.org/10.1016/j.foodres.2015.03.019.
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