LWT - Food Science and Technology 130 (2020) 109701

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LWT - Food Science and Technology

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Effects of candelilla wax/canola oil oleogel on the rheology, texture, thermal T

properties and in vitro starch digestibility of wheat sponge cake bread
J. Alvarez-Ramireza,∗, E.J. Vernon-Cartera, Y. Carrera-Tarelaa, A. Garciab, C. Roldan-Cruzb
a
Departamento de Ingeniería de Procesos e Hidráulica, Universidad Autónoma Metropolitana-Iztapalapa, Apartado Postal 55-534, CDMX, 09340, Mexico
b
Facultad de Ciencias Químicas, Universidad Veracruzana, Zona Universitaria, Xalapa, Ver, Mexico

A R T I C LE I N FO A B S T R A C T

Keywords: The use of oleogels for replacing solid fats is a hot topic in the food industry. The objective of this work was to
Sponge cake partially or totally replace butter by candelilla wax/canola oil oleogel, and evaluate its effect on starch di-
Candelilla wax oleogel gestibility and texture of wheat sponge cake bread. Candelilla wax/canola oil oleogel/butter blends were made
Texture substituting butter in 0, 25, 50, 75 and 100% by the oleogel. Increased substitution levels of oleogel by butter
In vitro digestibility
produced batters with significantly reduced the viscoelastic properties (up to ~ 60–70%). Total butter sub-
stitution by oleogel decreased cakes hardness from 29.61 to 13.37 N, but increased cake specific volume from
1.91 to 1.98 cm3/g. FTIR analysis indicated the formation of hydrated and short-range crystallized starch
structures at the expense of a reduction of amorphous domains, with the short-range ordering increasing by
about 120%. Oleogel incorporation had a positive effect on the in vitro starch digestibility, as the digestible
starch fraction increased from 70% to about 84%. Overall, the results showed that the use of oleogel for the
preparation of sponge cake imposes a trade-off problem between improving the textural properties or increasing
starch digestibility.

1. Introduction
Conventional fat-based shortenings (e.g., butter, margarine and
vegetal fat) are commonly used in the bread fabrication for imprinting
desired textural, sensory and shelf-life characteristics. For instance,
butter provides particular aromatic and textural properties that are
appreciated by consumers. Commonly, conventional shortening agents
contain large fractions of saturated and trans-fatty acids. However,
these components have been tagged as undesired food ingredients given
the negative effects for human health, including high levels of low
density lipoproteins causing cholesterol-raising or atherosclerosis
(Morio, Fardet, Legrand, & Lecerf, 2016). It has been highlighted that
low-density lipoproteins are the primary target for reduction of a di-
versity of problems linked to the so-called metabolic syndrome disease
(Wadhera, Steen, Khan, Giugliano, & Foody, 2016). In this regard, a
suitable strategy is to reduce the ingestion of food products with high
levels saturated and trans-fatty acids. An approach is replacing the
traditional fat-based shortening agents by others based on unsaturated
fats, which are less pernicious for human health (Makarewicz-Wujec,
Dworakowska, & Kozłowska-Wojciechowska, 2018).
Commonly, unsaturated fats (e.g., palmitoleic, oleic, myristoleic
and linoleic acids) are present in liquid phase under mild conditions.
This feature imposes some difficulties for the incorporation of un-
saturated fats in food products. For instance, fluid oils lead to some
negative textural and sensorial characteristics in bread products, as
stickiness and an oily palatability. An approach for achieving this is
converting a liquid oil into a gel-like material without modifying the
chemical characteristics of oil (Patel & Dewettinck, 2016; Toro-Vazquez
et al., 2007). This structuring is achieved by supramolecular assemblies,
usually gelator molecules, that entrap large amounts of oil into a gel-
like structure, resulting in a self-standing, thermo-reversible and three-
dimensional gel network with robust viscoelastic properties (García-
Andrade et al., 2020; Patel & Dewettinck, 2016). Oleogels can be easy
handled for their incorporation in the preparation of food products,
including ice creams, cooked frankfurters, cookies and sausages. Di-
verse edible materials like glycerols, fatty acids and alcohols, waxes,
sorbitan mono-stearate, mixtures of fatty acids and alcohols, sorbitan
tri-stearate, lecithin, oryzanol, and ethylcellulose or multicomponent
mixtures of them have been explored as oleogelators (Davidovich-
Pinhas, Barbut, & Marangoni, 2016).
Application of oleogels in food has been reported in recent years
(Singh, Auzanneau, & Rogers, 2017). The use of rice bran wax/high-
oleic sunflower oil oleogel was explored as solid-fat replacer, resulting
in a light ice cream with good texture and appearance (Zulim-Botega,

∗
Corresponding author.
E-mail address: jjar@xanum.uam.mx (J. Alvarez-Ramirez).

https://doi.org/10.1016/j.lwt.2020.109701
Received 9 February 2020; Received in revised form 1 May 2020; Accepted 31 May 2020
Available online 04 June 2020
0023-6438/ © 2020 Elsevier Ltd. All rights reserved.
J. Alvarez-Ramirez, et al. LWT - Food Science and Technology 130 (2020) 109701

Marangoni, Smith, & Goff, 2013). The potential of edible oleogels in

dairy products to enhance their fatty acid profile was studied (Bemer,
Limbaugh, Cramer, Harper, & Maleky, 2016). The performance of rice
bran wax/high-oleic sunflower oil oleogel as fat replacer in cream
cheese was investigated (Park, Bemer, & Maleky, 2018). Bakery pro-
ducts where 15–45% shortening was replaced of by beeswax-based
oleogel produced properties comparable to those of the original pro-
ducts (Demirkesen & Mert, 2019a). Oleic acid-rich oleogels improved
the fat profile of Bologna-type sausages, without affecting their sensory
characteristics (da Silva et al., 2019). Dry-cured sausages were prepared
with two oleogels, a mixture of γ-oryzanol and β-sitosterol and
beeswax, at two levels of replacement (20% and 40%) of pork backfat.
The fatty acid profile was improved in terms of nutrition (Franco et al.,
2020). The rehydration capacity of air-dried noodles was improved
when they were made with oleogels (Jung, Oh, Lee, & Lee, 2020). The
use of edible oleogels in bakery products which traditionally are made
with large amount of saturated fats is of particular interest given their
widespread consumption worldwide. An excellent overview of the
functions of shortening in bakery products was recently published
(Demirkesen & Mert, 2019b). Kim, Lim, Lee, Hwang, and Lee (2017)
found that replacing shortening by up to 25% with canola oil/carnauba
wax oleogels produced cakes with lower levels of saturated fatty acids
without quality loss. The replacement of commercial margarine with
oleogels produced muffins with improved spreadability, higher specific
volume, similar hardness values, and a more connected and homo-
geneous crumb structure (Giacomozzi, Carrín, & Palla, 2018). Stearoyl
lactylate based oleogels imitated the typical functionality of the crys-
talline network structures formed by triacylglycerol in bread products Fig. 1. (a) Storage (G′) and loss (G″) moduli of oleogel/butter blend variations.
(Meng, Guo, Wang, & Liu, 2019). Ethylcellulose oleogels can produce (b) Changes in the storage and loss moduli with the oleogel content. Square: O0,
breads with a stable soft texture (Ye, Li, Lo, Fu, & Cao, 2019). Saturated Circle: O25, Triangle: O50, Side Triangle: O75, Star: O100. Open Symbol: G′,
fat content was from 71 to 25% in bread make with oleogel (Jung, Oh, Closed Symbol: G’‘.
Lee, & Lee, 2020). Despite all the above studies, there are still important
issues to be explored such as the effect of oleogels in the generation of 2.2. Oleogel preparation
smell prints in bread during storage.
Of particular importance is the effect of partial or total replacement Candelilla wax (5 g) was added to canola oil (95 g) and the mixture
of shortenings by oleogels on the digestibility of the main bread com- was heated at 160 °C, followed by continuous stirring (200 rpm) for
ponents (starch, proteins and lipids). There are very few studies dealing 10 min (Toro-Vazquez, Charó-Alonso, Pérez-Martínez, & Morales-
with this topic. For instance, Limpimwong, Kumrungsee, Kato, Yanaka, Rueda, 2011). The mixture was allowed to stand at room temperature
and Thongngam (2017) showed that gel structuring is a key contributor overnight.
to a decrease in lipid digestibility. However, to our knowledge studies
about the effects of oleogels on the digestibility of starch, the main
component in bread, are still lacking. Thus, the aim of this study was to 2.3. Batter and cake preparation
evaluate the effect of replacing butter, partially or totally, by candelilla
wax/canola oil oleogel on the in vitro starch digestibility and textural Batter preparation included 700 g wheat flour, 420 g fresh milk,
characteristics of sponge cake. 350 g pasteurized whole eggs, 630 g sugar and 21 g baking powder.
Blends of canola oil oleogel/butter (210 g) were prepared with the
following percentages of oleogel (0, 25, 50, 75, 100%). Blends were
2. Materials and methods coded as Ox, where the symbol “x” denotes the percentage of oleogel in
the blend. All ingredients were initially mixed during 1 min at speed 4,
2.1. Materials followed by 9 min at speed 6 with a Kitchen-Aid Professional mixer-
KPM5 (St. Joseph, MI, USA). The resulting batter variations were coded
Wheat flour (10.93 g/100 g protein, 2.12 g/100 g fat, 74.35 g/100 g as Bx where the letter “x” indicates the percentage of oleogel in the
carbohydrates, 2.87 g/100 g dietary fiber) was provided by Fabrica de oleogel/butter blend.
Harinas Elizondo (Mexico City, Mexico). Sugar, eggs, salt, and canola Cake batter (60 g) was placed into a circular (6 cm diameter, ca-
oil were obtained at a local Walmart supermarket (CDMX, Mexico). pacity 80 mL) metallic, lard coated pan and baked in an electric oven
Dried baker's yeast was purchased from Safmex S.A. de C.V. (Nevada for 30 min at 190 °C. Subsequently, the baked cakes were removed from
Brand, Mexico). Micronized high purity candelilla wax obtained from the pans, kept at room temperature for 1 h to cool down, and packed in
Euphorbia cerifera was supplied by Multiceras S.A. de C.V. (Monterrey, polyethylene bags to prevent drying. Seven cakes were obtained from
Mexico). Amyloglucosidase (AMG, A7095, from Aspergillus niger, 260 each batter. The resulting batter variatons were coded as Cx where “x”
U.mL−1), α-amylase (Product 86,250, from Aspergillus oryzae, powder, indicates the percentage of oleogel relative to the oleogel/butter blend
1.5 U.mL−1), and pancreatin (P1750, from porcine pancreas, 300 in Ox.
U.mL−1) were provided by Sigma-Aldrich Mexico (Toluca, Mexico). All
other reagents used were analytical grade and purchased from J. T. 2.4. Oleogel/butter and batter variations dynamic rheological properties
Baker (CDMX, Mexico). Distilled water was used in all formulations.
Rheology oscillatory analysis of the oleogels and batter variations
were conducted using a Physica MCR 300 rheometer (Physica

2
J. Alvarez-Ramirez, et al.
Fig. 2. (a) Storage (G′) and loss (G″) moduli of batters with different oleogel
content. (b) Amplitude % at which the crossover between moduli took place as
a function of oleogel content in batter variations. Square: B0, Circle: B25,
Triangle: B50, Side Triangle: B75, Star: B100. Letter above columns denotes sta-
tistically significant differences (p < 0.05).
Mebtechnik GmbH, Stuttgart, Germany), with cone-plate geometry
(rotating cone 50 mm diameter, cone angle 2°, gap 1.0 mm).
Measurements and sample preparation followed the guidelines by
Guadarrama-Lezama, Carrillo-Navas, Pérez-Alonso, Vernon-Carter, and
Alvarez-Ramirez (2016).
2.5. Cake volume and textural characteristics
The volume of each cake sample was estimated by the rapeseed
displacement method (AACC, 1998). Measurements were conducted 2 h
after baking, and the specific volume was estimated as the bread vo-
lume/bread weight ratio. Texture profile analysis was conducted with a
Brookfield texturometer CT3-4500 (AMETEK, Middleborough, MA,
USA) equipped with a cylinder probe (TA25/1000, D = 50.8 mm,
L = 20 mm). Measurements were made by following the method by
Guadarrama-Lezama et al. (2016).
2.6. Color measurements
The color parameters L*, a* and b* of the cake variations crumb
were measured with a Hunter Lab Colorimeter Model 45/0 L (Hunter
Associates Lab., Indiana, USA). L*, a* and b* are measures of lightness,
redness/greenness and yellowness/blueness, respectively. The instru-
ment was calibrated against a standard white tile (L* = 97.63,
a* = 0.78 and b* = 0.25). The L*, a*, b* values were provided by the
instrument software.
2.7. Thermal properties
Samples of dry crumb (~5.0 ± 0.05 mg) of the bread variations in
3
LWT - Food Science and Technology 130 (2020) 109701
Fig. 3. Effect of heating temperature on the (a) storage, and (b) loss moduli of
batters with different oleogel contents. Square: B0, Circle: B25, Triangle: B50,
Side Triangle: B75, Star: B100.
excess water (1:2 dry sample/water ratio) were scanned in a DSC
equipment (TA Instruments-Q1000, New Castle, USA) previously cali-
brated with indium. Samples were heated from 10 to 150 °C at a con-
stant heating rate of 10 °C/min. Experiments were done in duplicate.
2.8. Fourier transform infrared (FTIR) spectroscopy
Fourier transform infrared (FTIR) analysis (Spectrum 100,
PerkinElmer, Waltham, MA, USA) was performed on the sponge cake
variations. Measurements and sample preparation were made by fol-
lowing the method by Guadarrama-Lezama et al. (2016).
2.9. Starch in vitro digestibility
Cake sample (about 100 mg) was crumbled and incubated with
porcine pancreatic α-amylase (10 mg) and amyloglucosidase (3.3
IU.mL−1) in 4 mL of 0.1 M sodium maleate buffer (pH 6.0) in a shaking
water bath at 37 °C (120 min). Ethanol (96%) was to inactivate en-
zymes. The sample was centrifuged and the resulting precipitate was
washed with 50% ethanol. The glucose content of supernatant was
measured using a glucose oxidase-peroxidase (GOPOD) kit. The glucose
content was corrected by subtracting the glucose content of the non-
digested sample. The hydrolyzed starch was calculated as glucose
(mg) × 0.9. The rapidly digestible starch (RDS) and slowly digestible
starch (SDS) fractions were estimated according to the method by
Englyst, Kingman, and Cummings (1992). Specifically, the RDS was the
starch hydrolyzed within the first 20 min of incubation, and the SDS as
the starch digested between 20 and 120 min. The kinetics of in vitro
digestion was described by the model proposed by Goñi, Garcia-Alonso,
and Saura-Calixto (1997):
J. Alvarez-Ramirez, et al.
Fig. 4. (a) Images of cakes prepared with different oleogel content.
C (t ) = C∞ (1 − exp(−kH t )) (1)
here, C (t ) is the total hydrolyzed starch, C∞ is the equilibrium con-
centration, and kH is the hydrolysis rate constant. The concentration C∞
can be seen as the starch that resisted the hydrolysis reactions under the
specified enzyme conditions.
2.10. Statistical analysis
Experimental data was analyzed by means of one-way analysis of
variance (ANOVA) and a Tukey's test for a statistical significance
(p < 0.05). The analysis was carried out with the package SPSS
Statistics 19.0. All experimental measurements were done in triplicate,
unless otherwise stated.
3. Results and discussion
3.1. Rheology of oleogel/butter blends
Fig. 1 a presents the behavior of the storage and loss moduli with
respect to the strain amplitude. The case O0 corresponds to butter and
O100 to candelilla wax/canola oil oleogel. For relatively small strain
amplitudes, up to 0.1%, the behavior of the oleogel blends was New-
tonian. After a transition region, the moduli underwent a fast decline
that reflects the disruption of the blend microstructure as induced by
large shear deformations. G′ predominated over G″ over the whole
strain amplitude range. Both the storage (G′) and loss (G″) moduli de-
creased about 4–5 magnitude orders for large strain amplitudes, up to
1000%.
Over the whole strain amplitude range, the butter exhibited the
higher G′ and G″ values, than oleogel/butter blends or the oleogel
alone. The decay of the G′ and G″ for large strain amplitudes followed a
power-like behavior ~γ −n . The power exponent for O0 (pure butter) was
n = 1.9 for G′ and n = 1.6 for G’‘. O100 (pure oleogel) presented the
smallest moduli values, with a pattern similar to the butter, while the
oleogel/butter blends displayed intermediate moduli values. Fig. 1 b
presents the change in G′ and G″ with respect to the blend composition.
The transition between the butter and pure oleogel behavior is almost
linear, which suggests that blend components do not contain important
molecular interactions. That is, the rheology of the oleogel/butter
blends satisfies a simple mixing rule for both the storage and the loss
moduli.
3.2. Rheology of batter variations
Fig. 2 a presents the behavior of the G′ and G″ of the different batter
variations. The incorporation of oleogel reduced the values of the vis-
coelastic moduli over the scrutinized strain amplitude range. The re-
duction was about threefold B0. Besides, the transition from an elastic
(G’ > G″) to a viscous behavior (G’ < G″) depended on the oleogel/
4
LWT - Food Science and Technology 130 (2020) 109701
butter ratio (Fig. 2b). In fact, the strain amplitude crossover decreased
with the fraction of candelilla wax/canola oil oleogel in the blend was
higher. This means that oleogel led to weaker microstructures, which in
turn increased flowability of the batter. Kim et al. (2017) reported that
the use of oleogel in batters reduced their viscoelasticity. Lim et al.
(2017) found that batters incorporating larger amounts of oleogel
showed lower viscosity, greater shear-thinning behavior and less elastic
nature.
The results shown in Fig. 2 were conducted at room temperature. An
interesting issue is the behavior of the batter viscoelasticity with tem-
perature. Fig. 3 presents the changes undergone by G’ (Fig. 3a) and G’’
(Fig. 3b) upon being subjected to a temperature ramp. The moduli of
the batter made with butter (B0) suffered as sharp decrease as the
temperature achieved about 50 °C. This effect might be associated to
the butter melting (about 37 °C), leading to a batter with a liquid-like
consistency. As the temperature increased beyond 50 °C, the viscoe-
lastic moduli exhibited an important recovery, mainly by the storage
modulus. This effect is due maybe to the interaction of batter compo-
nents (e.g., amylose-lipid complex formation and partial gelatinization
of starch granules). The batter made with the oleogel/butter blend
having the lowest fraction of oleogel (B25) presented a pattern similar to
the batter B0, although the viscoelastic moduli were slightly higher.
Increasing fractions of oleogel in the oleogel/butter blends, e.g. B75or
when pure oleogel (B100) was used in the batter, the decrease of the
viscoelastic moduli upon heating was dampened. It is noted that for
relatively high temperatures (about 75–80 °C), all batter variations
presented similar values of the viscoelastic moduli, which suggests that
the viscoelasticity of heated batters was probably dominated by other
effects related with, e.g., partial gelatinization of starch granules
(Sakiyan et al., 2011).
3.3. Cake specific volume
Fig. 4 shows images of the different cake variations. In general, the
oleogel addition produced cakes with acceptable appearance in terms of
structure and geometry. The effects of the oleogel addition on the
specific volume of cakes are shown in Table 1. In general, the cakes
containing oleogel had higher specific volume than the control made
with pure butter, implying that higher oleogel contents increased the
gas retention capacity of the batters. A negative correlation between
consistency and rising rate of bubbles in the cake bulk during the
baking process has been reported by some authors. For instance, Lebesi
and Tzia (2011) showed that batters with relatively high consistency
limited the mobility of bubbles, leading to cakes with reduced specific
volume. Similarly, Meng et al. (2019) showed that oleogels from so-
dium stearoyl lactylate-based lamellar crystals produced more compact
bread network structures. The results in Table 1 are in line with the
results in Fig. 2, which showed that increasing oleogel fractions in the
oleogel/butter blends produced batters with decreased storage (G′) and
loss (G″) moduli. The addition of candelilla wax/canola oil oleogel
J. Alvarez-Ramirez, et al. LWT - Food Science and Technology 130 (2020) 109701

Resilience × 101 (−)

0.03cd
0.03bc
0.04d

0.04b
0.03a
±
±
±
±
±
1.83
1.86
1.92
2.03
2.12
1.24cd
1.23d

1.33b
1.31a
1.29c
Chewiness (N)

±
±
±
±
±
52.64
54.71
55.73
69.31
77.02
Cohesiveness × 101 (−)

0.25ab
0.19b

0.23a
0.23c
0.17c
±
±
±
±
±

Values are means ± standard error, of three replicates. Superscripts with different letters in same column indicate significant differences (P ≤ 0.05).
4.62
4.73
4.98
5.06
5.17
Adhesiveness × 101 (mJ)

0.23de
0.24d

0.33b
0.32a
0.29c
±
±
±
±
±
1.81
2.23
3.48
5.10
6.67
Specific volume, color and texture parameters of cakes added with different levels of candelilla wax/canola oil oleogel.

Fig. 5. (a) Example of endothermic heat flow for cakes. (b) Effect of oleogel
content in peak temperatures, and (c) enthalpies. Letter above columns denotes
1.62ab

1.65cd
1.62d
1.43a

1.48c

statistically significant differences (p < 0.05). Open circle: First peak; closed
Hardness (N)

circle: Second peak.

±
±
±
±
±
29.61
25.22
17.98
15.39
13.37

reduced the batter consistency which allowed for an improved uniform

rising of bubbles in the cake bulk.
0.61b
0.72b
0.68a
0.67a
0.61c

3.4. Cake texture

±
±
±
±
±
b* (−)

10.91
11.64
11.84
12.27
12.68

Texture is an important issue for consumer acceptance of baked

products. The effect of the oleogel supplementation in cake texture is
shown in Table 1. As the oleogel content increased, the hardness of
cakes decreased. A negative correlation between specific volume and
0.09a,b
0.11b
0.06a
0.06a

0.09c

hardness has been reported (Sabanis, Lebesi, & Tzia, 2009). The present
study confirmed the inverse relationship between volume and hardness
±
±
±
±
±
a* (−)

(r = − 0.95, p < 0.05). In fact, cakes having lower specific volume

6.82
6.63
6.42
6.21
5.97

exhibited higher hardness levels. A possible explanation is linked to the

amount of bubbles retained by batter in the baking process (Gómez,
0.56a
0.41a
0.59a
0.47a
0.49a

Moraleja, Oliete, Ruiz, & Caballero, 2010). In this way, smaller cakes, in
general, exhibit denser and more packed crumb structure, which results
±
±
±
±
±

in harder cakes (Sabanis et al., 2009). Adhesiveness, cohesiveness,

L* (−)

87.51
88.45
88.98
87.94
87.76

chewiness and resilience were also measured, and they all increased as
oleogel content increased. In particular, the cohesiveness increase im-
plies that cakes containing oleogel exhibited greater resistance to
Specific Volume (cm3/g)

crumbling. These results are in line with a previous report showing that
oleogel addition led to improved texture of sweet pan bread (Jung
et al., 2020).
0.07b
0.08a
0.07a
0.08c
0.07c

3.5. Cake crumb color

±
±
±
±
±
1.91
1.89
1.94
1.97
1.98

The values of the L*, a*, b* parameters exhibited by the cake var-
iations crumb are presented in Table 1. Replacing butter by oleogel
induced slight increases (but non-significant) in the value of the L*
Sample
Table 1

C100

parameter. L* values ranging from 0 to 100, provide an approximate

C25
C50
C75
C0

measurement of luminosity (Guadarrama-Lezama et al., 2016). All the

5
J. Alvarez-Ramirez, et al.
Fig. 6. (a) FTIR spectrum of cakes with different oleogel content. The variation of the (a) 995/1022, (c) 1047/1022, and (d) β-sheets/coils ratios obtained from
deconvolution of the FTIR signal. Letter above columns denotes statistically significant differences (p < 0.05).
cake variations crumb presented L* values above 87. It has been re-
ported that consumers scored pound cake with high luminosity as “I
like very much” in a hedonic sensory test (Sánchez-Pardo, Ortiz-
Moreno, García-Zaragoza, Necoechea-Mondragón, & Chanona-Pérez,
2012). The values exhibited for a* and b* by the cake variations crumb
were positive, and tended to significantly decrease for a* and to in-
crease for b* as oleogel content was increased. These color changes can
be attributed to the change induced in physicochemical properties of
the cakes induced by replacing butter by oleogel. Esteller and Lannes
(2008) stated that changes in the physicochemical characteristics ba-
kery products is known to be determinant in their color characteristics.
3.6. Differential scanning calorimetry (DSC)
DSC analysis was used to gain insights on the effect of the oleogel
fraction in the cake thermal properties. Fig. 5 a illustrates the en-
dothermic heat flow pattern of a cake sample. An endothermic transi-
tion was observed in the 50–85 °C range. This peak has been ascribed to
amylopectin melting and gelatinization effects (Zeleznak & Hoseney,
1987). A second smaller peak occurred in the 90–110 °C range and
represents the dissociation of amylose-lipid complexes (Biliaderis, Page,
Slade, & Sirett, 1985). The effect of the oleogel fraction in the estimated
peak temperatures of the two endothermic peaks is exhibited in Fig. 5 b.
The first peak temperature showed only a slight positive trend. In
6
LWT - Food Science and Technology 130 (2020) 109701
contrast, the second peak temperature shifted to the left, although no
important statistical differences were detected. The enthalpy of the
corresponding endothermic peaks is presented in Fig. 5 c. The enthalpy
of the first peak is about 4-fold the enthalpy of the second peak. Besides,
the enthalpy of the first peak showed no statistical differences with
respect to the oleogel content, indicating that the starch gelatinization
processes were hardly affected by the fat substitution. In contrast, the
enthalpy of the second endothermic peak showed a visible reduction
with the oleogel incorporation. If one considers the enthalpy as an
index of the amylose-lipid complex content (Biliaderis et al., 1985), the
result in Fig. 5 c indicates that the oleogel reduced the formation of
complexes in the cake.
3.7. FTIR analysis
FTIR analysis was carried out to assessing the interactions between
the cake components. Fig. 6 a presents the FTIR spectrum of the dif-
ferent cake variations. The wide peak at about 3290 cm−1 is generally
linked to N–H bending vibrations of gluten proteins. The peak at about
2930 cm−1 is ascribed to lipids, and also to the formation of lipid-starch
complexes (Chen et al., 2018). The intensity band with a peak at about
1637 cm−1 is ascribed to Amide I groups, which results from the C]O
stretching vibrations of the peptide bond. The peak with small intensity
at 1550 cm−1 is usually linked to Amide II protein groups. On the other
J. Alvarez-Ramirez, et al.
Fig. 7. (a) Enzymatic hydrolysis kinetics of starch in cakes with different oleogel content. Square: C0, Circle: C25, Triangle: C50, Side Triangle: C75, Star: C100. (b)
Limiting hydrolysis advance, and (c) hydrolysis rate constant obtained by least-squares fitting of the hydrolysis kinetics. (d) Digestible starch fractions of starch in
cakes with different oleogel content. Gray Column: RDS, Light Gray Column: SDS. Letter above columns denotes statistically significant differences (p < 0.05).
hand, the peak close to 1400 cm−1 resulted from protein side-chain
COO-. The wide band centered at 1015 cm−1 is related to C–O and C–C
stretching, and C–O–H bending associated to carbohydrates. The region
at about 1080–950 cm−1 is linked to the molecular organization of
starch chains. Of particular interest are the ratios 995/1022 and 1047/
1022, which are related to the content of hydrated and short-range
crystalline domains relative to amorphous domains in starch chains
(van Soest, Tournois, de Witt, & Vliegenthart, 1995) Fig. 6b and 6 c
presents the FTIR ratios 995/1022 and 1047/1022, respectively. Both
ratios increased as the oleogel content was increased, suggesting that
the oleogel promoted the formation of hydrated and short-range crys-
tallized starch structures at the expense of a reduction of amorphous
domains. On the other hand, the Amide I region provides important
insights on the secondary structure of proteins (e.g., gluten) contained
in cake variations. The issue is important as protein digestibility
(Carbonaro, Maselli, & Nucara, 2012) and gluten network structure
(Gao, Tay, Koh, & Zhou, 2018) are affected by the secondary structure.
Numerical deconvolution of the Amide I showed that the signal is well-
described by two Gaussian functions, corresponding to β-sheet struc-
tures and random coils. Fig. 6 d presents the fluctuation of the ratio β-
sheet/coils with the as oleogel amount increased. Only slight variations
were observed. This suggests that oleogel addition did not affect the
secondary structure of gluten-related proteins. In turn, this result would
imply that the variations of specific volume and textural properties are
7
LWT - Food Science and Technology 130 (2020) 109701
more linked to the mobility of bubbles.
3.8. In vitro digestibility
The experimental data of the enzymatic hydrolysis of starch for the
different cake variations are shown in Fig. 7 a. The progress trajectories
exhibited an exponential-like behavior, characterized by an initial fast
hydrolysis phase, and a saturation phase where the hydrolysis achieved
a limiting value. The progress curve can be described by the model
given by Eq. (1). The results of the least-squares fitting are presented in
Fig. 7b and 7 c for the limiting hydrolysis advance C∞ and the hydro-
lysis rate constant kH . The parameter C∞ decreased as the oleogel
content increased, indicating that blending increasing amounts of
oleogel with butter produced a more extensive enzymatic hydrolysis of
starch chains. The hydrolysis rate constant kH showed slight variations
with relative to the oleogel content. This means that the amount of
oleogel hardly affected the velocity at which starch was digested. Ac-
cording to Englyst et al. (1992) method, the digested starch fractions
can be classified in terms of two sub-fractions known as rapidly di-
gestible starch (RDS) and slowly digestible starch (SDS). Fig. 7 d ex-
hibits the variation of the RDS and SDS fractions with the oleogel
content. Interestingly, the SDS fraction remained statistically un-
changed (p < 0.05), while the RDS fraction increased significantly
(p < 0.05) with the oleogel content. The mechanisms behind the
J. Alvarez-Ramirez, et al.
results in Fig. 7 d are not clear at all. Fig. 6 showed that the short-range
crystallinity of starch chains increased as the oleogel content was in-
creased. It is known that crystalline structures are harder to be hydro-
lyzed (Lau, Zhou, & Henry, 2016). However, the results in Fig. 7 d
exhibited the opposite trend. Although short-range ordering of starch
chains might affect the enzymatic hydrolysis, this is not the dominating
factor. On the other hand, oleogel content affected negatively the
amylose-lipid complex content as reflected by a reduction of the en-
thalpy values in Fig. 5 c. Amylose-lipid complexes function as resistant
starch fraction. In fact, it has been reported that complexed amylose is
hydrolyzed and adsorbed to the same extent as free amylose but at
slower rates (Holm et al., 1983). This finding is consistent with the
results shown in Fig. 7 b where the amount of SDS decreased with the
oleogel fraction.
4. Conclusions
This work explored the effect of substituting partially or completely
butter by canola oil/candelilla wax oleogel in the properties of sponge
cakes. The underlying idea was that canola oil is less pernicious for
human health as it contains a large amount of unsaturated fatty acids.
Oleogels offer some advantages. For instance, cakes made with in-
creasing amounts of oleogel displayed increasingly lower hardness and
improved cohesiveness, which are textural attributes preferred by
consumers. However, their use exhibits some drawbacks. The results in
this study showed that the digestibility of starch, a major component of
cakes, might be increased. This poses a problem since increased starch
digestibility is commonly linked with the increase and prevalence of
human health illnesses associated with metabolic syndrome. In this
way, the use of oleogel for the preparation of sponge cakes imposes a
trade-off problem between textural properties and starch digestibility.
CRediT authorship contribution statement
J. Alvarez-Ramirez: Conceptualization, Investigation. E.J.
Vernon-Carter: Methodology. Y. Carrera-Tarela: Writing - review &
editing, Methodology. A. Garcia: Writing - review & editing. C.
Roldan-Cruz: Formal analysis.
Declaration ofcompeting interest
We wish to confirm that there are no known conflicts of interest
associated with this publication and there has been no significant fi-
nancial support for this work that could have influenced its outcome.
We confirm that the manuscript has been read and approved by all
named authors and that there are no other persons who satisfied the
criteria for authorship but are not listed. We further confirm that the
order of authors listed in the manuscript has been approved by all of us.
We confirm that we have given due consideration to the protection
of intellectual property associated with this work and that there are no
impediments to publication, including the timing of publication, with
respect to intellectual property. In so doing we confirm that we have
followed the regulations of our institutions concerning intellectual
property.
We understand that the Corresponding Author is the sole contact for
the Editorial process (including Editorial Manager and direct commu-
nications with the office). He/she is responsible for communicating
with the other authors about progress, submissions of revisions and
final approval of proofs. We confirm that we have provided a current,
correct email address which is accessible by the Corresponding Author
and which has been configured to accept email from jjar1963@gmail.
com.
8
LWT - Food Science and Technology 130 (2020) 109701
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