LWT - Food Science and Technology 101 (2019) 526–533

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LWT - Food Science and Technology

journal homepage: www.elsevier.com/locate/lwt

Characterization of spray drying microencapsulation of almond oil into taro T

starch spherical aggregates
J.D. Hoyos-Leyvaa,1, L.A. Bello-Pereza,∗, J.E. Agama-Acevedoa, J. Alvarez-Ramirezb,
L.M. Jaramillo-Echeverryc
a
Centro de Desarrollo de Productos Bióticos, Instituto Politécnico Nacional, Km. 8.5 Carr, Yautepec-Jojutla, Colonia San Isidro, Apartado Postal 24, Yautepec, Morelos,
62731, Mexico
b
Departamento de Ingeniería de Procesos e Hidráulica, Universidad Autónoma Metropolitana-Iztapalapa, Apartado Postal 55-534, Iztapalapa, CDMX, 09340, Mexico
c
Programa de Ingeniería Agroindustrial, Universidad La Gran Colombia seccional Armenia, Ciudadela del Saber la Santa María Km. 7 vía Armenia - La Tebaida, Armenia,
Quindío, Colombia

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

Keywords: Taro starch spherical aggregates have good potential as wall material for microencapsulation of hydrophobic
Spherical aggregates compounds. This study considered these spherical aggregates for protection of almond oil against oxidative
Encapsulation efficiency stress. Encapsulation efficiency, microcapsules morphology and physical and chemical stability of the micro-
Thermodynamics capsules were determined. The total encapsulation efficiency (TE) was 56.0 ± 0.6%, while the effective en-
Integral entropy
capsulation efficiency was 37.5 ± 0.5%. The size of the microcapsules was in the range 1.6–31.1 μm, with
Oil oxidative stability
porous structure that allows the flow of solvents through the intraparticle cavities. It was found that the almond
oil was located mostly in the internal cavities of the spherical aggregates. Spray drying induced an increase in the
peroxide value of the almond oil at the time of microencapsulation, which in turn enhanced the chemical sta-
bility. The maximum physical stability of the microcapsules was found around 8.2 g∙100 g−1 of moisture content
for temperatures in the range 25–45 °C of storage. Overall, the results showed that the spherical aggregates
provide protection against oxidation reactions to microencapsulated almond oil.

1. Introduction cosmetic and food goods. The interest in almond oil has been motivated
from the reported benefits in human health, such as reduction of the
The recent years have witnessed the growing interest in the design incidence of colon cancer and cardiovascular benefits, related to the
and production of food, pharmaceutic and cosmetic products con- increase in high density lipoproteins (HDL). Other reported benefits
taining natural and functional vegetal bioactive compounds. A re- include immunity-boosting, anti-inflammatory and anti-hepatotoxic
cognized approach to produce and protect ingredients with natural effects (Ahmad, 2010). Almond oil is a material susceptible to oxidative
bioactive compounds is microencapsulation, which is a procedure for reactions, due to its high content of unsaturated fatty acids (Sanahuja,
facilitating bioactive compounds manipulation while increasing the Moya, Pérez, Teruel, & Carratalá, 2009). In this sense, the micro-
shelf life of products. Vitamins, pigments, volatile compounds, and encapsulation of almond oil can be important for the development of
essential oils are examples of functional and natural bioactive com- new products. Diverse wall materials have been used for encapsulation
pounds commonly microencapsulated. In particular, the interest for the of oils, for example isolated and concentrated proteins (Mohammed,
microencapsulation of essential oils relies on the fact that these com- Tan, Manap, Alhelli, & Hussin, 2017; Quispe-Condori, Saldaña, &
pounds are susceptible to oxidation reactions induced by adverse con- Temelli, 2011), gums (Beristain, Azuara, & Vernon-Carter, 2002;
ditions, such as light, humidity, temperature and oxygen presence. The Fernandes, Borges, & Botrel, 2014; Frascareli, Silva, Tonon, &
instability of bioactive compounds is commonly reflected as loss of the Hubinger, 2012; Fuchs et al., 2006), maltodextrins (Bae & Lee, 2008;
nutritional quality of the whole product and the development of un- Munoz-Ibanez et al., 2016), chemically modified starch (Anwar & Kunz,
desirable odors. 2011; Sharif et al., 2017; Silva, Vieira, & Hubinger, 2014), en-
Almond oil is an essential oil widely used for the production of zymatically modified-porous starch- (Lei et al., 2018), and starch

∗
Corresponding author.
E-mail address: labellop@ipn.mx (L.A. Bello-Perez).
1
Present address: Programa de Ingeniería Agroindustrial, Fundacción Universitaria Agraria de Colombia, Calle 170 No. 54a-10, Bogotá, D.C., Colombia.

https://doi.org/10.1016/j.lwt.2018.11.079
Received 16 July 2018; Received in revised form 22 November 2018; Accepted 24 November 2018
Available online 25 November 2018
0023-6438/ © 2018 Elsevier Ltd. All rights reserved.
J.D. Hoyos-Leyva et al. LWT - Food Science and Technology 101 (2019) 526–533

spherical aggregates (Zhao & Whistler, 1994). The extensive research washes were made with 20 ml of hexane to the sample retained on the
with different walls materials can be explained from the variability in filter paper. The solvent was evaporated at 60 °C and the extracted oil
the microencapsulation efficiency (29–94%), size (1-1000 μm) and weight was recorded (Tan, Chan, & Heng, 2005). The total oil content
morphology of the microcapsules, as well as the protective effect of- was determined in a Soxhlet extraction unit (B-812, Büchi Labortechnik
fered by the wall materials to the microencapsulated oils. In this sense, AG, CH, Ettlingen, DE). The extractions were carried out with petro-
walls materials with high activation energy to bring major protection to leum ether and 25 cycles. The encapsulated oil (AOE) was quantified by
oils against oxidative degradation are highly desired. In recent studies, the difference between the total oil (AOT) and the surface oil (AOS). The
the thermodynamic properties of taro starch spherical aggregates were total encapsulation efficiency (TE) was computed as follows:
analyzed (Hoyos-Leyva, Bello-Pérez, & Alvarez-Ramirez, 2018), AOT
showing the potential as protection against oxidative reactions, com- TE (%) = × 100
AO0 (1)
monly seen in the oils degradation. The rationale behind the advantage
of taro starch over starch from other botanical sources is its ability for where AO0 is the almond oil added to the spray dryer feed dispersion.
forming spherical aggregates. In fact, Debet and Gidley (2007) found The effective encapsulation efficiency (EE) was calculated with the
that protein content determines the integrity of insoluble remnants (i.e., following equation:
ghosts) after gelatinization. More specifically, proteins act as bonding AOE
agent for maintaining the cohesion of starch granules. However, in EE (%) = × 100
AO0 (2)
many cases the fraction of proteins is not sufficient to stabilize the
structure of spherical aggregates, and external bonding agents (e.g.,
gum Arabic, carboxymethyl cellulose and carrageenan) should be 2.3. Morphology and size distribution
added. Taro starch is an interesting case where the fraction and possibly
the nature of proteins lead to the formation and stabilization of sphe- The morphology of almond oil microcapsules was assessed by va-
rical aggregates. Recently, Gonzalez-Soto, de la Vega, García-Suarez, cuum scanning electron microscopy (SEM-LV). The conditions of the
Agama-Acevedo, and Bello-Pérez (2011) reported that taro starch can microscope were adjusted according to what was reported by Hoyos-
form spherical aggregates without the addition of bonding agents. Leyva, Bello-Pérez, Yee-Madeira, Rodriguez-Garcia, and Aguirre-Cruz
Isolated taro starch contains a relatively high content of protein (about (2017).
50–70 g/kg), which is sufficient for bonding starch granules within a The particle size distribution of the microcapsules was measured
spherical configuration. with a Mastersizer 3000 instrument (Malvern Instruments Limited,
Spherical aggregates offer some advantages for microencapsulation Malvern, Worcestershire, GB) equipped with a Malvern Aero S acces-
of functional compounds. However, systematic studies for assessing the sory for analysis of dry powders. Air pressure, feed, maximum feed flow
stability of spherical aggregates in the face of, e.g., storing conditions and obscuration were 1 × 105 Pa, 30%, 58 m s−1, 0.5–8.0%, respec-
have not been reported. Results in this line should provide valuable tively.
information on the potential of spherical structures made of starch
granules and chains for diverse applications in food products. In this 2.4. Almond oil location in microcapsules
regard, this work considered the microencapsulation of almond oil, a
model hydrophobic core material, in taro starch spherical aggregates The location of retained almond oil was observed using a confocal
and the evaluation of the encapsulation efficiency, microcapsules laser scanning microscope (LSM 710 NLO, Carl Zeiss Microscopy
morphology, and the physical and chemical stability of the retained oil. GmbH, Jena, DE). The instrument conditions were “stack” scan mode,
filters 417–729, and the laser light beam at 405 nm (50.0%), 561 nm
2. Materials and methods (6.5%), 468 (7.5%) and 633 nm (8.0%). The nile red fluorochrome was
used to observe fluorescence of the retained oil.
2.1. Almond oil microcapsules production
2.5. Fourier transformed infrared spectroscopy with attenuated total
Taro starch was isolated from corms of Colocassia esculenta var. reflectance (FTIR-ATR)
Esculenta. The starch isolation process was carried by following the
methodology proposed by Gonzalez-Soto et al. (2011). The isolated Bulk almond oil, taro starch spherical aggregates and almond oil
starch was washed with distilled water and filtered (0.841 mm), and the microcapsules were analyzed by FTIR-ATR using a Vertex 70 FT-IR
concentration of solids in the starch dispersion was adjusted to (Bruker Optik GmbH., Ettlingen, DE) equipped with an ATR accessory
20.0 g∙100 mL−1 water. To determine the effect of oil concentration on with a diamond crystal at incidence angle of 45°. The experiment was
the encapsulation efficiency, the almond oil was added in a proportion carried out following the methodology proposed by Sanahuja et al.
of 10 and 20 g∙100 g−1. The starch-oil dispersion was homogenized in (2009). Briefly, the resolution was 4 cm−1, wavenumber range
an Ultra-turrax (T25 digital ULTRA-TURRAX, IKA Werke GmbH & Co. 400–4000 cm−1 and 128 scans. The spectrum analysis was done di-
KG, Baden-Württenberg, DE) at 8000 rpm for 10 min. The starch dis- rectly from the instrument software (OPUS v. 7.5, Bruker Optik GmbH.,
persion was fed to a Mini Spray Dryer (Model B-290, BÜCHI UK Ltd, Ettlingen, DE).
Chadderton, UK) equipped with a double flow atomizer. The spray
drying conditions were 145 °C for the air inlet temperature, and 2.6. Peroxide value (PV)
10.6 g min−1 for feed rate. During the drying process, the dispersion
was continuously stirred to achieve homogeneity in the feed flow. The The almond oil microcapsules and bulk almond oil (4.7 g) were
dried powder was stored in a glass container to further analysis. stored in amber flasks with a hermetic seal in an oven at 65 °C to
evaluate the change of peroxides content, which is related to lipids
2.2. Total (TE) and effective (EE) encapsulation efficiency oxidation. The peroxide value was measured every week; an aliquot
was taken and analyzed completely to avoid experimental errors caused
The encapsulation efficiency was determined by quantifying the by the treatment of the sample. To this end, 2.0 g of microcapsules was
amount of total and surface oil in the microcapsules. The surface oil was used to extract the retained oil by washing with hexane and repeated
determined from 2.0 g of sample, which were weighed in a 50 ml Falcon vortex shaking. The peroxide value was determined following the
tube. About 25 ml of hexane were added and vortexed for 2 min. The methodology proposed by Karaca, Low, and Nickerson (2013), with
mixture was filtered through a filter paper (Whatman No. 1). Two slight modifications. Briefly, the oil was recovered in a 125 ml flask,

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15 ml of a mixture of acetic acid: chloroform (3:2) and 0.250 ml of a Table 1

saturated potassium iodide solution were added. Immediately, the Total (TE) and effective (EE) encapsulation efficiency, moisture content and
sample was shaken vigorously in a vortex for 1 min. Subsequently, water activity of almond oil microcapsules.
15 ml of distilled water and 0.25 ml of a starch indicator solution Almond Oil Concentration (g ∙ 100 g−1)
(1.0 g∙100 mL−1 water) were added. The mixture was titrated with so-
dium thiosulfate (0.001 N) until the purple color disappeared. The ali- 10.0 20.0
quots of bulk almond oil were treated in the same way. A blank pre-
TE (%) 56.0 ± 0.5a 55.6 ± 1.2a
pared with the mixture of all the reagents was used for each PV EE (%) 37.5 ± 0.5a 45.0 ± 0.6b
measurement, and the blank titration volume was used in the quanti- Moisture (g ∙ 100 g−1) 3.47 ± 0.21a 2.79 ± 0.22b
fication of PV. The peroxide value was calculated by the following aw 0.10 ± 0.01a 0.08 ± 0.01a
equation (Karaca et al., 2013):
Values are the mean of three replicates ± SE. Different letter in row indicate
statistical differences (p < 0.05).
(S − B ) × N × 1000
PV =
W (3)
3. Results and discussions
where S is the volume of sodium thiosulfate titrated in the sample, B is
the titration volume of the blank, N is the normality of the thiosulfate 3.1. Total and effective encapsulation efficiency of almond oil in taro starch
(0.001 mol L−1), and W is the sample weight (extracted oil). spherical aggregates

The total (TE) and effective (EE) encapsulation efficiency of almond

2.7. Oxidative stability index oil in taro starch spherical aggregates by spray drying were summarized
in Table 1. Samples prepared with the two initial oil concentrations
The oxidative stability index was determined on a Rancimat in- added to the spray dryer feed dispersion did not exhibited differences in
strument (Metrohm 679, Metrohm AG, Herisau, CH). The conditions the total encapsulation efficiency. However, differences were observed
were adjusted to that reported by Silva et al. (2014) and the re- in the effective encapsulation, which was greater for samples with an
commendations of the Cd 12b-92 method of the American Chemical initial oil concentration of 20.0 g∙100 g−1. This effect can be explained
Oils Society (AOCS, 2009). The air flow was 20 l h−1, the analysis by the oil packaged in the porous cavities of the spherical aggregates,
temperature was 120 °C, the sample weight was 3 g for the bulk almond thus reducing the easy extraction of the oil during the washing with the
oil and 0.5 g of the almond oil microcapsules. The change in water solvent. The relative low values of the EE can be due to the porous
conductivity influenced by the dissolved volatile oxidation products structure of the spherical aggregates, which does not limit the flow of
was quantified. the solvent through its internal porous structure and facilitated the
extraction of oil located in the internal cavities produced by the ag-
gregation of granules. Values of total encapsulation efficiency of oils
2.8. Physical stability of almond oil microcapsules obtained from different vegetable and animal sources have been re-
ported in the range 29–85% (Bae & Lee, 2008; Carneiro, Tonon, Grosso,
The physical stability of the microcapsules was evaluated from the & Hubinger, 2013; Fernandes et al., 2014; Fuchs et al., 2006; Quispe-
water vapor adsorption isotherms. To this end, the moisture and water Condori et al., 2011). Also, Quispe-Condori et al. (2011) reported that
activity (aw) at the minimum integral entropy value were calculated. relatively low wall:core material ratios in the spray dryer feed disper-
The experimental conditions of water vapor adsorption isotherms were sion resulted in large fractions of surface oil. These results contrast with
adopted from the reported by Hoyos-Leyva, Agama-Acevedo, Bello- the almond oil microcapsules results in this study since a greater
Perez, Vernon-Carter, and Alvarez-Ramirez (2016) using an Aquadyne amount of initial oil resulted in a higher amount of oil retained in the
DVS-1 instrument (Quantachrome Instruments, Boynton Beach, Florida, spherical aggregates. Such differences can be attributed to the char-
US). The change in integral entropy (ΔSint) was obtained from sorption acteristics of the wall materials used in both works, because the sphe-
data at constant spreading pressure, which resulted in the application of rical aggregates of taro starch do not form a continuous film as done by
the following equation (Pérez-Alonso, Beristain, Lobato-Calleros, other wall materials commonly used in microencapsulation (e.g., pro-
Rodríguez-Huezo, & Vernon-Carter, 2006): teins and maltodextrin). On the other hand, the total encapsulation
efficiency of taro starch aggregates was of the order of 50–55%
ΔHint (Table 1). Several studies with other wall materials (e.g., proteins,
ΔSint = Ss − Sl = − R ln(a w )
T (4) maltodextrin) reported values in the range 25–90%, with the highest
values for protein (e.g., WPI). The values reported in our study are in
Where Ss = S/Nl is the integral entropy of the water adsorbed in the the range of those reported in the specialized literature. The main ad-
microcapsules (kJ ∙ mol−1K−1), Sl is the differential entropy of the vantage of taro starch spherical aggregates is their relatively low cost
water adsorbed in the microcapsules, T is the absolute temperature (K), (proteins are about 5–10 times more expensive than starch) and easy
ΔSint is the integral enthalpy at the temperature T (K), R is the universal processing. In fact, the formation of taro starch spherical aggregates
gas constant (kJ ∙ mol−1K−1), and aw is the water activity from the does not require the addition of bonding agents.
sorption data.

3.2. Moisture content and water activity

2.9. Statistical analysis
The moisture content and the water activity reflect the efficiency of
All measurements were done by triplicate. The mean and the stan- the spray drying process and affect the quality of the dry powder. Low
dard error (SE) were reported. Statistical differences were determined moisture content and water activity due to the deterioration of the
with a p value < 0.05. Tukey or Dunnet comparative mean test was product is prevented by chemical reactions related to the presence of
carried out (in the cases of comparison of the microcapsules with the free water, physical changes or undesired microbiological activity. The
bulk almond oil as control). Statistical analysis was performed using values for moisture content and water activity are reported in Table 1.
JMP version 10.0 (SAS Institute Inc., Cary, NC, US). The values were low and similar to the reported for microcapsules of
oils retained in different wall materials (Fernandes et al., 2014; Fuchs

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Fig. 1. SEM-LV micrography of almond oil microcapsules (10%) a) 2,000×; b) 4,992×; c y d) 10,000×.

et al., 2006; Karaca et al., 2013; Turchiuli et al., 2005). The results
indicated an efficient drying process.

3.3. Morphology and particle size distribution

The morphology of the almond oil microcapsules was observed by

SEM-LV (Fig. 1). Fig. 1 a displays the spherical structure of the mi-
crocapsules as influenced by the aggregation effect of the taro starch
granules during spray drying process. The microcapsules exhibited a
large diversity of sizes and porous surfaces, related to the polyhedral
and irregular shape of the taro starch granules (Agama-Acevedo et al.,
2011). On the other hand, the varied sizes of the pores can be observed
in Fig. 1 b. SEM-LV images show that almond oil did not fill the porous
cavities of the spherical aggregates. The particle size distribution of the
taro starch granules and the microcapsules was shown in Fig. 2,
showing monomodal distribution. The mean particle size of taro starh
granules was about 4.0 μm, and increased after spray drying. In fact, the
average size of the almond oil microcapsules was higher than the par-
ticle size of taro starch granules, and smaller than the size of taro starch
spherical aggregates. It should be recalled that the estimation of the Fig. 2. Particle size distribution of taro starch (continuous line), almond oil
particle size distribution was made after dispersing the spherical ag- microcapsules (dot-dashed line) and taro starch spherical aggregates (dashed
line).
gregates in water. The results in Fig. 2 indicate that the spherical ag-
gregates are effectively dispersed in water without disrupting the ag-
gregation structure. In fact, the oil contained in the spherical aggregates Comparing the results of particle size against other oil microcapsules,
imprinted hydrophobic properties, such that the otherwise agglomer- the values reported here are lower than those reported for linseed oil
ated powder can be easily dispersed in an aqueous medium. The wide retained in mixtures of commercial wall materials such as Capsul®-
range of particle size (1.6–31.1 μm) of spherical aggregates was in line maltodextrin, Hi-Cap®-maltodextrin, whey protein concentrate and gum
with the observed in Fig. 1 a. This range may be related to the ag- Arabic (Carneiro et al., 2013), sunflower oil in porous starch
gregation of a lower number of starch granules or also to non-ag- (Belingheri, Ferrillo, & Vittadini, 2015) and modified starch mixed with
gregated starch granules. The particle size is an indicator of the type of inulin for the retention of oregano oil (Zabot, Silva, Azevedo, &
products in which the microcapsules can be applied, since human can Meireles, 2016). The microcapsules range reported for those materials
perceive “sand” particles larger than 8 μm (Singer & Dunn, 1990). exhibited sizes from 1 to 1000 μm.

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Fig. 3. Confocal laser scanning microscopy images: microencapsulated almond oil autofluorescence (a), light microscopy (b) and superposition a and b (c) of almond
oil microcapsules.

3.4. Almond oil location in microcapsules

Oil was not located mostly on the surface of the microcapsules

(Fig. 3). However, oil was also located in the intraparticle cavities
formed by the aggregation of the starch granules (arrows in Fig. 3c).
Some difficulties were confronted for the staining of particles with
fluorochrome because it was an aqueous solution, causing the disin-
tegration and movement of the microcapsules when observed in the
microscope. Images obtained with confocal microscopy corroborated
the hypothesis proposed for the observed difference of values of total
efficiency and effective encapsulation (Table 1), in which a significant
reduction of efficiency was detected as a consequence of the superficial
washes of the microcapsules for quantification of the surface oil.

3.5. Attenuated total reflectance fourier transform infrared spectroscopy

Fig. 4 shows the ATR-FTIR spectrum of the bulk almond oil, taro
starch spherical aggregates and the almond oil microcapsules. Bulk
almond oil showed peaks in wavenumber 2952, 2921, 2852, 1456,
1375 and 719 cm−1. The band 2952 cm−1 has been ascribed to the
Fig. 4. ATR-FTIR spectrum of bulk almond oil (black line), taro starch spherical
vibration of the C = CH bonds present in the unsaturated fatty acids
aggregates (red line), almond oil microcapsules (blue line).
(Hernández & Zacconi, 2009). The peak at wavenumber 2921 and
2852 cm−1 represent the asymmetric and symmetric extension vibra-
tions of aliphatic functional groups CH2, respectively. Comparison be- to the stretching of C-H bonds, while the change in the 1535 cm−1 band
tween the peaks observed in the taro starch spherical aggregates and (Amide II) was due to structural changes in the residual protein in the
almond oil microcapsules, an increase in the absorbance of the band spherical aggregates (Gholizadeh et al., 2014). The FTIR analysis in-
2918 cm−1 can be observed for the microcapsules and the dis- dicated that spray drying did not induce chemical interactions between
appearance of the peak in the band 1535 cm−1 in the taro starch taro starch (wall material) and almond oil (core material). It is sug-
spherical aggregates. The increase in the 2918 cm−1 band corresponded gested that the retention of almond oil into the porous cavities of taro

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more and deeper space for oil retention. In turn, this feature helped to
reduce the stress conditions affecting negatively the functional prop-
erties of almond oil.

3.7. Oxidative stability index (OSI)

The oxidative stability of the bulk almond oil and almond oil mi-
crocapsules were tested with the active oxygen method in a Rancimat
instrument. The induction time, also known as oxidative stability index
(OSI), for commercial almond oil was 13.1 ± 0.9 h, while for almond
oil microcapsules the OSI was > 48 ± 0.2 h. Besides, the PV values for
fresh microcapsules was about 15 mEq O2/Kg, and increased linearly
with the storage time. However, the PV increase was reduced by mi-
croencapsulation in spherical aggregates. In fact, the PV values after 6
weeks for spherical aggregates were about 20 mEq O2/Kg, and about 80
mEq O2/kg for microcapsules. This result indicated that the micro-
encapsulation by spherical aggregation process reduced the oxidation
reactions in the almond oil, prolonging its shelf life. It is apparent that
the almond oil was retained in a greater proportion in the internal
cavities of the spherical aggregates, achieving an increase in the OSI.
Fig. 5. Peroxide value of almond oil microencapsulated within taro starch The OSI found for the bulk almond oil was similar to values reported by
spherical aggregates (closed square) and bulk almond oil (open square) stored Maestri et al. (2015) and Moayedi, Rezaei, Moini, and Keshavarz (2011)
at 65 °C. for almond oil isolated from different cultivars (11.1–13.5 h), with
variations attributed to the different content of α-tocopherol (396 and
starch spherical aggregates was more to physical effects (e.g., ca- 630 μg g−1 oil). Also, Silva et al. (2014) microencapsulated coffee oil by
pillarity), rather than to chemical interactions. spray drying using combinations of wall materials such as mal-
todextrins and commercial modified starches (Hi-Cap®, Capsul®, N-
Lok®), reporting increases in OSI up to 8.9 h, a value that is smaller than
3.6. Peroxide value that found to the almond oil microencapsulated in taro starch spherical
aggregates (> 34.8 h). Such difference may be related to the positive
The initial peroxide value of the commercial almond oil used for effect of the aggregation of the taro starch granules, suggesting that this
microencapsulation was 5.6 ± 0.2 meq ∙ kg−1, while for the micro- wall material could be a material with potential for commercial use in
encapsulated oil PV was 13.2 ± 0.4 meq ∙ kg−1. The peroxide value of the protection of essential oils against oxidation reactions. The pro-
almond oil isolated from different cultivars has been reported in the tection against oxidation provided by the taro starch spherical ag-
range of 7.5–15.6 meq ∙ kg−1 (Özcan, Ünver, Erkan, & Arslan, 2011). gregates may be related to its relative high activation energy
Spray drying caused an increase in the initial peroxide value in the (28 kJ mol−1K−1) reported in a previous work (Hoyos-Leyva et al.,
encapsulated oil (Fig. 5). However, taro starch spherical aggregates 2018). Additionally, the porous structure of taro starch spherical ag-
provided protection against oxidation reactions, an effect reflected in gregates limited the oxygen molecules (O2) permeation from outer
the reduced peroxide value found in the microcapsules up to week 6 surface to the inner cavities of aggregates, due to the relatively high
(Fig. 5). The increase in the peroxide value caused by the micro- quantity of hydroxyl groups (OH) of glucose units conforming the
encapsulation process by spray drying has been reported for crude palm polymer chains (amylose and amylopectin) of the starch granules
oil (Ferreira et al., 2016), flaxseed oil (Tonon, Grosso, & Hubinger, structure. In fact, hydroxyl groups are involved in the formation of
2011), fish oil (Aghbashlo, Mobli, Madadlou, & Rafiee, 2013), among hydrogen bonds with O2 molecules, resulting in an effective reduction
others. This effect of increasing the peroxide value can be attributed to of the oxidation of the core material (Wakabayashi, Kondo, Domen, &
the relatively high energy input by the air inlet temperature in the dryer Hirose, 1997).
(145 °C). Serfert, Drusch, Schmidt-Hansberg, Kind, and Schwarz (2009)
reported that an increase in the drying temperature from 160 to 210 °C 3.8. Physical stability of almond oil microcapsules
caused an increase in the peroxide value. The initial peroxide value in
the microencapsulated oil was in the range established in the Food The physical stability of the microcapsules was estimated from the
Codex for edible vegetable oils (< 15 meq∙kg−1). calculated data of integral entropy (see Eq. (4)), where the values of
The protection effect conferred by almond oil microcapsulation moisture and water activity corresponding to the minimum values of
against oxidation can be explained from the relatively reduced porosity the integral entropy were considered as the maximum stability condi-
of the material, which in turn limits the exposure of the oil to stress tions of the almond oil microcapsules. The results in Fig. 6 showed that
conditions in storage. The increase in the peroxide value in the mi- the values of minimum entropy were located above 8.0 g∙100 g−1 of
croencapsulated oil was influenced by diverse factors, including the moisture content for the three different temperatures (25, 35 and
direct thermal dissociation (thermolysis) caused by the storage tem- 45 °C). It can be also noted that the temperature had a positive effect in
perature (65 °C) (Frankel, 1980), the oxygen permeation through the the maximum stability moisture content, since the maximum stability
microcapsules (Ahn et al., 2008; Belingheri, Giussani, Rodriguez- moisture content increased with the temperature value. Jimenez,
Estrada, Ferrillo, & Vittadini, 2015; Wang, Tian, & Chen, 2011) which García, and Beristain (2004) reported that the peroxide value of con-
would induce oil autooxidation. Belingheri, Ferrillo, et al. (2015) and jugated linoleic acid encapsulated in whey protein concentrate was
Belingheri, Giussani, et al. (2015) reported the microencapsulation of higher compared to water activities > 0.6 at low water activity, an
sunflower oil in porous starch, finding that the peroxide value of the effect that could be related to the entropy behavior found to almond oil
retained oil in the porous starch was similar to that for the spray-dried microcapsules. This behavior has been explained from the physical state
free oil. This effect was attributed to the pore diameter (1–10 μm) in the (vitreous to low water activity) of the wall material, since it was ex-
modified starch. Compared to microcapsules made of modified porous pected that oxidation reactions could be zero in this state. However, the
starch (Belingheri, Ferrillo, et al., 2015), spherical aggregates offer presence of oxygen, size heterogeneity of the microcapsules and their

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