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Botanical Origin as a Determinant for the

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Starch/Strke 2016, 68, 18 DOI 10.1002/star.201600143 1

RESEARCH ARTICLE

Botanical origin as a determinant for the mechanical properties

of starch films with nanoparticle reinforcements
Sergio Martinez, Clarisse Rivon, Omar P. Troncoso and Fernando G. Torres

Department of Mechanical Engineering, Catholic University of Peru, Lima, Peru

Starches were extracted from three varieties of native Andean potatoes (Solanum tuberosum var Received: April 29, 2016
amarilla, Solanum tuberosum sbsp. Andigena var huamantanga, and Solanum tuberosum sbsp. Revised: May 26, 2016
Andigena var tomasa). Starch-based nanocomposite lms were prepared using starch as the Accepted: May 27, 2016
matrix and starch nanoparticles as the reinforcement at 3, 5, and 7 wt%. The mechanical
properties of the prepared nanocomposites were assessed by tensile tests. The results show that
the mechanical properties of the nanocomposite lms vary depending on both the amount of
reinforcement present, and the botanical origin of the starch. In addition, the highest increases
of elastic moduli (up to 1.53 times) are found when a lms matrix and reinforcement
nanoparticles are prepared from a single botanical source.

Keywords:
Botanical origin / Native Andean starch / Starch nanoparticles

: Additional supporting information may be found in the online version of this article at the publishers web-site.

1 Introduction reduces the degradation of starch and enables thermoplastic

Starch is a natural polysaccharide found in the roots, seeds,
steams, and tubers of an array of different plants including
corn, potato, wheat, and rice. Starch granules are formed by
two polymers: amylose and amylopectin. Amylose is a linear
polymer and composes 2030% of the total starch granule. It
is formed by long chains of a-(1, 4)-linked D-glucose units
with a degree of polymerization ranging from 3
102 to
1
104 [1]. In contrast, amylopectin is a branched polymer
consisting of a-(1,4)-linked glucose chains joined by a -(1,6)-
linkages with a degree of polymerization of about 108 [2].
Starch has received attention for its potential as a
biodegradable thermoplastic attained through processing
with the addition of a plasticizer, such as water or glycerol.
According to Dufresne [3], the addition of a plasticizer
Correspondence: Dr. Fernando G. Torres, Department of Mechanical
Engineering, Catholic University of Peru, Lima 32, Peru
E-mail: fgtorres@pucp.edu.pe
Fax: 51 1 6262461
Abbreviations: AFM, atomic force microscopy; E, elastic modulus
of the reinforced films; Em, elastic modulus of the non-reinforced
matrix; POT1, golden potato; POT2, Huamantanga potato;
POT3, white potato; Rr, reinforcement ratio; SEM, scanning
electron microscopy; UTS, ultimate tensile stress
starch to be processed under mild conditions.
Plasticized starch shows limited potential in industrial
applications due to its low resistance to mechanical
stresses [4]. Many studies have reported the preparation of
starch reinforced with materials, such as nanoclays [5, 6],
natural bers [710], cellulose nanobers [11, 12], and
mineral nanoparticles, among others. Increased concern for
the environmental impact of new technologies has led to
increased interest in the development of biodegradable
nanollers for the production of completely biodegradable
nanocomposites.
Starch, as a natural renewable resource, is a prime
candidate for the development of a novel nanoller. Wang
et al. [13] embedded starch nanocrystals of waxy maize starch
in a waterborne polyurethane matrix. They found out that the
reinforced lms with 1 wt% of starch content had a higher
tensile modulus (E 1 MPa), compared to unreinforced
lms (E 0.5 MPa). Le Corre et al. [14] found that with the
increase of starch reinforcement, there was also an increase
in tensile modulus. They tested a natural rubber matrix
with 5 wt% of waxy maize starch (E 1.6 MPa) and 10 wt%
(E 2.5 MPa).
Colour online: See the article online to view Figures in colour.

2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.starch-journal.com

2 S. Martinez et al.
Starchstarch nanocomposites (starch matrix reinforced
with starch nanoparticles) are thought to benet from the
chemical similarities between the matrix and the reinforce-
ment. The resulting enhanced stress transfer between the
matrix and the reinforcement improves the nal performance
of the nanocomposite [15]. In the past, starchstarch nano-
composites have been prepared using waxy maize starch as
both the matrix and the reinforcement [1517]. Cassava and
rice starch have also been used in a similar manner [18, 19].
Theoretical models were used to predict the mechanical
properties of starch lms to compare with the experimental
results; the Voigt and Reus model [20, 21], HalpinTsai
model [22, 23], and Hashin and Shtrikman model [24] were
used in this study.
In this study we used starches extracted from three
varieties of Andean potatoes. Acid hydrolysis was utilized to
obtain crystalline starch nanoparticles, and a cast process
was used to prepare starch lms reinforced with starch
nanoparticles at 3, 5, and 7 wt%. The main objective of this
study, was to determine the effect of botanic origin on the
thermal and mechanical properties of these lms.
2 Materials and methods
2.1 Materials
2.1.1 Starch extraction
The starches used in this study were extracted from three
different varieties of Andean potatoes as listed in Table1.
The amylose content of the starches, as measured by a
colorimetric procedure [25], was 28.05  0.63% for POT1,
22.40  1.06% for POT2, and 28.34  6.32% for POT3.
Starch was extracted according to the method reported by
Torres et al. [26]. All chemicals used were of analytical grade.
The potatoes were cleaned with tap water and rinsed
with distilled water. In a blender sleeve, the samples were
homogenized and left for decantation for 4 h using distilled
water. The supernatant was discarded and the precipitates
were dissolved again. White precipitates were degreased in a
suspension of methanol (J.T. Baker, cat. no. JT9093-3) and
water (1:1). The residue was decanted again for 1 h, allowing
Table 1. Code, common name, and scientific designation of the
starch extracted and used in this study
Code Common name Scientific designation
POT1 Golden potato Solanum tuberosum var amarilla
POT2 Huamantanga potato Solanum tuberosum sbsp. Andigena
var huamantanga
POT3 White potato Solanum tuberosum sbsp. Andigena
var tomasa
2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Starch/Strke 2016, 68, 18
the remaining starch to precipitate to the bottom of the
container. The resulting starch was dried at 40C for 48 h
and stored in a desiccator at room temperature (20C).
2.1.2 Preparation of starch nanoparticles
Starch nanoparticles were prepared according to the method
reported by Angellier et al. [27]. A total of 11.75 g of
starch underwent degradation with 80 mL of H2SO4 3.16 M
(MerckMillipore, cat. no. 100731) at 40C under magnetic
agitation for 5 days. Afterwards, the nal suspension was
centrifuged. The precipitate was washed by successive
centrifugation and re-dispersion in distilled water until it
reached a neutral pH. Finally, starch nanoparticles were
redispersed in 100 mL of distilled water (16 mg/mL), and
stored at 4C. Nanoparticles were prepared from the three
starch sources listed in Table 1. Nanoparticle yield, calculated
as the amount of nanoparticles recovered per 100 g of
processed dry starch, was 13.53% for POT1, 14.65% for
POT2, and 17.36% for POT3.
2.1.3 Preparation of starch films
Starch lms were prepared following the procedure outlined
in Torres et al. [28]. This process partially hydrolyzes starch in
order to increase the amount of linear chains present in the
solution. These linear chains interact through hydrogen
bonding, and form lms with enhanced mechanical
properties [29]. Dried starch was diluted in distilled water
to form a 5% starch solution. This solution was partially
hydrolyzed in dilute hydrochloric acid (0.1 N) (Merck
Millipore, cat. no. 100317), bringing the pH to 2.0. Glycerol
was added at ratio of 2:5 (glycerol:starch (dry basis)), and the
starch solution was homogenized by stirring for 15 min at
95C. Afterwards, the solution was neutralized in dilute
sodium hydroxide (0.1 N) (J.T. Baker, cat. no. JT3722-19),
which brought the pH to ten, and stopped hydrolysis. The
neutralized solution was cooled to 40C. The composite lms
were prepared by adding the suspension of starch nano-
particles in the desired quantities (3, 5, and 7% w/w relative
to the total mass, starch plasticizer nanocrystals). After
the addition of the nanoparticles, the solution was stirred for
10 min at room temperature (20C). Finally, the solution
was spread on Petri dishes and dried in an oven at 40C
for 16 h. Films from the three different starch sources were
prepared at a thickness of 200 mm with nanoparticle
reinforcement contents of 0, 3, 5, and 7% (Table 2).
2.2 Characterization techniques
The mechanical properties of the starch nanocomposite
lms were determined by tensile tests. A benchtop tensile
testing machine (ESM Mark-10), equipped with a 10 N
(0.5%) load-cell, was used for these experiments. Four
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Starch/Strke 2016, 68, 18 Botanical origin as a determinant for the mechanical properties of starch films 3

Table 2. Starch-based nanocomposites prepared in this study ratio, crystallinity, and gelatinization temperature [30, 31].
The size of the nanoparticles extracted varied depending on
Matrix Reinforcement Sample code the variety of Andean potato starch. The starch from POT1
POT1 POT1/0
exhibited nanoparticles with diameters of 88  73 nm, POT2
POT1 POT1/3-POT1 starch contained particles of 77  26 nm, and POT3 starch
POT1 POT1/5-POT1 produced larger nanoparticles of 218  127 nm in size [32].
POT1 POT1/7-POT1 According to Corre et al. [33], nanoparticles extracted
POT2 POT1/3-POT2 by acid hydrolysis are derived from the crystalline part of
POT2 POT1/5-POT2
hydrolyzed starch granules. Starch granules are formed by
POT2 POT1/7-POT2
POT3 POT1/3-POT3
amorphous and crystalline lamellae (9 nm) that contain
POT3 POT1/5-POT3 amylose and amylopectine chains. These lamellae are
POT3 POT1/7-POT3 organized in blockets (2050 nm) that form amorphous
POT2 POT2/0 and crystalline rings (100500 nm) [34, 35]. Acid hydrolysis
POT1 POT2/3-POT1 disrupts the structure of starch granules and renders nano-
POT1 POT2/5-POT1
particles with a crystallinity of about 45% [33].
POT1 POT2/7-POT1
POT2 POT2/3-POT2
In order to prepare the lms, a diluted solution of starch
POT2 POT2/5-POT2 (5 wt%) was heated to 95C. This heating triggers the
POT2 POT2/7-POT2 gelatinization of starch. During gelatinization, the starch
POT3 POT2/3-POT3 granules swell, leach amylose, and lose their crystalline
POT3 POT2/5-POT3 structure as their ordered regions melt [36]. We introduced
POT3 POT2/7-POT3
starch nanoparticles to the lms after gelatinization to
POT3 POT3/0
ensure that their crystalline regions remained intact. Figure 1
POT1 POT3/3-POT1
POT1 POT3/5-POT1 shows the AFM micrographs of the external topography of a
POT1 POT3/7-POT1 representative unreinforced lm and a reinforced composite
POT2 POT3/3-POT2 lm. The starch nanoparticles cannot be observed.
POT2 POT3/5-POT2 In our previous report [32], we used DSC tests to assess
POT2 POT3/7-POT2 structural differences between different varieties of potato
POT3 POT3/3-POT3
starch and potato starch nanoparticles. We found that the
POT3 POT3/5-POT3
POT3 POT3/7-POT3 endothermic peak temperature of starch nanoparticles
(80C) is higher than the peak temperature of starches
(60C). We associated this increased melting temperature
samples were tested for each type of reinforcement and cut of starch nanoparticles with an increase in crystallinity.
into strips of 5 mm
50 mm. The crosshead speed was set In contrast, the DSC tests performed here (Table 3)
to 10 mm/min and the tests were performed at room showed no clear difference between the pure starch lms and
temperature (1520C). Youngs modulus, ultimate tensile the starchstarch nanoparticle lms, probably due to the low
strength (UTS), and maximum strain were measured. nanoparticle content in the composites.
DSC experiments were carried out in a PerkinElmer DSC We then evaluated the mechanical properties of the
4000 calorimeter. Stainless steel hermetic pans were used. starch-based lms. Table 4 shows the elastics modulus,
About 10 mg of the nanocomposite lms were cut into small the ultimate tensile stress (UTS), and the strain at break of
pieces and put inside the pans. Temperature scans from 25 to the starchstarch samples. The mechanical properties
400C were performed at 5C/min. All measurements were of the non-reinforced samples produced from POT2
carried out under a nitrogen atmosphere (20 mL/min). Peak and POT3 starches are similar. The elastic modulus of
temperatures were calculated with Pyris Thermal Analysis the POT2/0 and POT3/0 samples are 5.25  0.35 GPa and
Software. 4.90  0.53 GPa, respectively. In contrast, the elastic
Statistical tests performed include the analysis of variance modulus of the POT1/0 samples is lower, at 2.58 GPa.
(ANOVA) and the StudentNewmanKeuls method for The UTS and strain at break of POT01/0 samples were also
pairwise comparisons. The null hypothesis was rejected at a lower when compared to the values of the POT2/0 and
signicance level of 0.05. POT3/0 samples. Previous studies, from this laboratory [26]
have reported similar morphological and physical proper-
ties for POT1, POT2, and POT3 starches, including starch
3 Results and discussion granule size (20 mm), amylose content (26%), and
gelatinization temperature (63C). This suggests that
The botanical origin determines important properties of the differing mechanical properties of the lms may be
starches, such as grain size and shape, amylose/amylopectin accounted for by variance in botanical origin.

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4 S. Martinez et al. Starch/Strke 2016, 68, 18

Table 3. Temperatures characterized by endothermic peaks

during differential scanning calorimetry tests

Sample Peak temperature (C)

POT1/0 138.80  5.55a

POT1/3-POT1 129.54  5.18a
POT1/5-POT1 128.84  1.57a
POT1/7-POT1 129.02  7.97a
POT1/3-POT2 138.59  8.56a
POT1/5-POT2 125.47  3.71a
POT1/7-POT2 134.36  2.51a
POT1/3-POT3 128.56  10.22a
POT1/5-POT3 126.11  9.37a
POT1/7-POT3 98.35  12.82a
POT2/0 116.46  2.39a
POT2/3-POT1 132.03  2.71a
POT2/5-POT1 119.19  3.32a
POT2/7-POT1 125.89  4.07a
POT2/3-POT2 139.53  2.95a
POT2/5-POT2 128.55  9.32a
POT2/7-POT2 125.39  4.78a
POT2/3-POT3 130.57  2.10a
POT2/5-POT3 136.56  8.99a
POT2/7-POT3 136.75  0.73a
POT3/0 117.90  1.94a
POT3/3-POT1 125.92  1.09a
POT3/5-POT1 130.12  2.74a
POT3/7-POT1 131.39  8.46a
POT3/3-POT2 129.31  2.88a
POT3/5-POT2 129.03  2.56a
POT3/7-POT2 115.75  19.86a
POT3/3-POT3 126.43  8.03a
POT3/5-POT3 131.94  7.93a
POT3/7-POT3 126.69  4.47a

Values are mean  SD. Letters indicate significantly different

groups (StudentNewmanKeuls pairwise comparisons).

Figure 1. AFM micrographs of a POT1/0 film (a) and a POT1/3-

POT1 nanocomposite film.
The elastic modulus of the lms increased with an
increasing level of reinforcement. This result is in agreement
with previous studies of starchstarch nanocomposites
(starch matrix reinforced with starch nanoparticles)
[25, 29]. The experimental values of elastic modulus obtained
from tensile test were compared with theoretical values
from the Voigt and Reus model, HalpinTsai model, and
Hashin and Shtrikman model (see Supporting Information).
Figure 2 shows representative curves of theoretical values
calculated. All of the models predict an increase in the elastic
modulus value with an increasing degree of reinforcement.
It is worth noting that the experimental values are higher
than the values calculated with the models. The proposed
similarity between the chemical structures of the matrix and
the reinforcement is suggested to promote good miscibility,
and strong interfacial adhesion. X-ray diffraction tests
suggested that this optimal interaction between the starch
matrix and the reinforcement may be due to crystallization
present along the interface [29].
In order to assess the extent of the increase of elastic
modulus, a reinforcement ratio (Rr) has been calculated
as follows:
E
Rr 1
Em
where E stands for the elastic modulus of the reinforced
sample and Em stands for the elastic modulus of the non-
reinforced matrix.
Figure 3 shows the reinforcement ratios of all samples.
The reinforcement ratio is higher for the samples produced
with POT1 starch and ranges from 1.63 to 3.00, whereas, it
ranges from 1.64 to 2.40 for the samples produced with
POT3 starch. The elastic modulus of the samples produced
with POT2 starch had the lowest increment among the

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Starch/Strke 2016, 68, 18 Botanical origin as a determinant for the mechanical properties of starch films 5

Table 4. Elastic modulus, ultimate tensile strength (UTS), and matrices used, ranging from 1.11 to 1.50. Variability among
strain at break determined from uniaxial tensile tests
samples from different botanical origin should be consid-
ered as a possible cause. In a previous study, the elastic
Sample Elastic modulus (GPa) UTS (MPa) Strain at break (%)
modulus of pure starch lms from 12 different Andean
POT1/0 2.58  0.45a 0.41  0.07a 0.17  0.06a starches was measured [28]. The elastic modulus of the
POT1/3-POT1 4.2  0.65b 1.19  0.04b 0.49  0.08b lms prepared with POT2 starch was the lowest among
POT1/5-POT1 5.98  0.48c 1.49  0.19c 0.54  0.11b six different varieties of Andean potatoes.
POT1/7-POT1 7.75  1.44d 1.69  0.24d 0.41  0.14b For most of the samples, the reinforcement ratio
POT1/3-POT2 5.12  0.32b 1.18  0.18b 0.41  0.09b
increased as the reinforcement content increased. The
POT1/5-POT2 6.35  0.83c 1.49  0.15c 0.47  0.07b
analysis of the reinforcement ratio values suggests that the
POT1/7-POT2 6.56  0.31d 1.91  0.07d 0.64  0.08b
POT1/3-POT3 5.99  0.78b 0.57  0.07e 0.12  0.01a reinforcement ability of POT3 nanoparticles was higher than
POT1/5-POT3 7.05  0.37c 1.00  0.21b 0.20  0.37a POT1 and POT2 nanoparticles, at 3 and 5% nanoparticle
POT1/7-POT3 5.19  0.19d 1.59  0.17d 0.47  0.10b content. It is expected that reinforcements with small
POT2/0 5.25  0.35e 1.18  0.16c 0.40  0.13b diameter nanoparticles have a high total surface area, and
POT2/3-POT1 5.59  0.11b 1.24  0.20c 0.33  0.06a consequently, an enhanced reinforcing effect. Our results,
POT2/5-POT1 5.82  1.13c 2.25  0.56f 0.29  0.13a
however, seem to contradict this as nanoparticles obtained
POT2/7-POT1 7.34  0.82d 1.38  0.27c 0.30  0.17a
from POT3 starch had the largest average diameter (220 nm)
POT2/3-POT2 5.64  0.33b 1.21  0.06c 0.39  0.7b
POT2/5-POT2 6.05  0.16c 1.38  0.06c 0.39  0.05b when compared with nanoparticles obtained from POT1
POT2/7-POT2 7.00  0.51d 1.91  0.16d 0.60  0.13b and POT2 (75 and 85 nm).
POT2/3-POT3 5.85  0.08b 1.27  0.01c 0.50  0.02b Figure 3 also shows that the highest reinforcement ratio
POT2/5-POT3 6.66  0.33c 1.46  0.05c 0.45  0.6b was found for the POT1/7-POT1 samples (POT1 matrix
POT2/7-POT3 7.90  0.31d 1.68  0.09d 0.35  0.03b and POT1 reinforcement). The reinforcement ratio of
POT3/0 4.90  0.53e 1.26  0.16c 0.45  0.13b
POT3/7-POT3 samples was also the highest among samples
POT3/3-POT1 8.68  0.87f 1.31  0.13e 0.20  0.01a
produced with POT3 starch matrix. In the case of the
POT3/5-POT1 9.43  0.52g 1.37  0.09c 0.23  0.04a
POT3/7-POT1 9.99  0.27h 1.55  0.04d 0.27  0.03a samples produced with POT2 matrices, the value of the
POT3/3-POT2 8.02  1.16f 1.54  0.06b 0.29  0.03b reinforcement ratio is similar for all the reinforcements
POT3/5-POT2 8.26  0.13g 1.52  0.12c 0.30  0.02b used. These results suggest that the best reinforcement is
POT3/7-POT2 10.04  0.41h 1.15  0.16b 0.15  0.04b achieved when the samples are produced with the same
POT3/3-POT3 9.00  2.52f 1.91  0.19c 0.42  0.2b starch for the matrix as for the reinforcement.
POT3/5-POT3 9.56  1.65g 1.97  0.13b 0.48  0.02b
Previous studies [37] have found that botanical source
POT3/7-POT3 11.75  0.76h 1.64  0.31d 0.28  0.10b
greatly affects the composition and functional properties of
Values are mean  SD. Letters indicate significantly different starch, including its gelatinization properties, X-ray diffrac-
groups (StudentNewmanKeuls pairwise comparisons).
tion pattern (A-, B-, or C-type) and amylopectin unit-chain
Ultimate tensile strength (UTS) and strain at break measured with
axial tensile tests. length. The degree of polymerization and the molecular
weight of amylose have also been shown to vary between
botanical sources [3840].

Figure 2. Theoretic calculation of the elastic modulus

(E) as a function of the reinforcement percentage of
POT3/POT3 samples for Voigt and Reus (&), Halpin
Tsai (~), and Hashin and Shtrikman (*) models.

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6 S. Martinez et al.
According to Angellier [41], starch nanocrystals used as
reinforcement form a three-dimensional network thanks
to hydrogen bonding forces. In the case of polysaccharide
lms processed via casting-evaporation, the formation of
such a network is responsible for the improvement of the
2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Starch/Strke 2016, 68, 18
Figure 3. (a) Variation of the reinforcement ratio (Rr),
as defined in Eq. (1), with the reinforcement
percentage for nanocomposites prepared with
POT1 matrix reinforced with POT1 (^), POT2 (*),
and POT3 (X) nanoparticles. (b) Variation of the
reinforcement ratio (Rr), as defined in Eq. (1), with the
reinforcement percentage for nanocomposites pre-
pared with POT2 matrix reinforced with POT1 (^),
POT2 (*), and POT3 (X) nanoparticles. (c) Variation
of the reinforcement ratio (Rr), as defined in Eq. (1),
with the reinforcement percentage for nanocompo-
sites prepared with POT3 matrix reinforced with
POT1 (^), POT2 (*), and POT3 (X) nanoparticles.
mechanical properties of the composites [41]. Angles and
Dufresne [42] have found evidence, that suggests that the
increase of the mechanical properties of starch lms
reinforced with cellulose whiskers could be accounted for
a transcrystallization phenomenon of the amylopectin
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Starch/Strke 2016, 68, 18 Botanical origin as a determinant for the mechanical properties of starch films
chains located near the cellulose whisker surface. This
restricts the mobility of the amorphous amylopectin chains
of the crystallite-coated cellulose whiskers, because crystal-
line domains of amylopectin.
The results found here, suggest that the chemical afnity
between the host matrix and the nanoparticles from the
same starch source play a key role in the reinforcing effect
of nanoparticles. Such afnity may create this favourable
interaction between matrix and nanoparticles at a molecular
level.
4 Conclusions
In this paper, starches from three different types of potatoes
were used to produce lms composed of both a matrix and
nanoparticles reinforcements. The mechanical properties of
the starchstarch nanocomposites produced were improved
through the addition of starch nanoparticles. The botanical
origin of the starches seems to play a key role in the
mechanical properties of the lms. The results show that the
highest increases of elastic moduli were obtained when
the host matrix, and its nanoparticle reinforcements were
produced from the same starch source. This demonstrates
the reinforcing mechanisms reliance on both nanoparticle-
nanoparticle and nanoparticle-matrix interactions.
5 Novelty statement
The reinforcing effect of starch nanoparticles on starch lms
is increased when the host matrix and the nanoparticles are
produced from starch of the same botanical origin.
The authors would like to thank the Peruvian Council of
Science and Technology (Concytec-FONDECYT) and the Vice-
Rectorate for Research of the Ponticia Universidad Catolica
del Peru (VRI-PUCP).
The authors do not have any conicts of interest.
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