J Food Sci Technol

[Link]

ORIGINAL ARTICLE

Modulating porosity and mechanical properties of pectin

hydrogels by starch addition
Flávia Souza Almeida1 • Karen Cristina Guedes Silva1 • Antônio Matias Navarrete de
Toledo1 • Ana Carla Kawazoe Sato1

Revised: 11 May 2020 / Accepted: 21 May 2020

Ó Association of Food Scientists & Technologists (India) 2020

Abstract The use of blends to produce hydrogels allows Introduction

modulating their characteristics as mechanical properties and
microstructure. This work aimed to study the properties of To protect sensible compounds, ensure stability and pro-
pectin and starch hydrogel blends. Pectin gel was homoge- mote controlled delivery, encapsulation has been a suc-
neous and porous, while pectin/starch blends containing 50% cessful technique. A number of methods such as ionotropic
or more pectin exhibited denser and closer network, indicating gelation, self-assembly, complex coacervation, among
that starch reduced the porosity of pectin network. Such others may be employed to encapsulate compounds (Burey
characteristic was associated with higher gel hardness, cohe- et al. 2008; Farjami and Madadlou 2017; Okuro et al.
siveness, firmness, and water holding capacity. The influence 2015); however, the most appropriate should be chosen
of total biopolymer concentration and type of process (ex- mainly based on the application, bioactive properties,
trusion and atomization) on particle formation were also available process scale and associated costs (Fujiwara et al.
evaluated indicating that among the tested formulations, 2013; Okuro et al. 2015). In addition, the modulation of
pectin 1% and starch 1% blend was the only sample able to microstructure using biopolymer blends is an alternative to
form particles under extrusion and atomization. The addition achieve different gel properties for application in encap-
of 5% (w/v) microparticles to the grape nectar presented no sulation systems.
influence on rheological parameters, maintaining the pseu- Ionotropic gelation is a technique used to produce soft
doplastic behavior. Both the starch addition and the amount of hydrogel particles that are desirable for addition on prod-
polymers used impacted the micro and macrostructure of ucts with high moisture content, generally due to their
pectin gels. ability to protect bioactive compounds and to act as texture
modifiers (Stokes 2011). This technique is based on the
Keywords Hydrogel  Mechanical properties  crosslinking of charged hydrocolloids with counter ions
Microparticle  Gelification  Biopolymer (Burey et al. 2008; Shewan and Stokes 2013). Biopoly-
meric solutions are generally dripped into counter ions
bath, in which salts diffuse inside the polymeric chain,
& Ana Carla Kawazoe Sato promoting the crosslinking of the structure that creates a
acksato@[Link] three-dimensional network (Patil et al. 2012).
Flávia Souza Almeida Low metoxilation pectin can be used to produce such
flaviasouzaudi@[Link] structures (De Moura et al. 2018; Ferreira et al. 2009;
Karen Cristina Guedes Silva Oidtmann et al. 2012); however, it presents high solubility,
karen_cgs@[Link] which is a disadvantage considering the early release of
Antônio Matias Navarrete de Toledo bioactive compounds from delivery structures (Cury et al.
matiasnavarrete@[Link] 2014; Liu et al. 2003). Therefore, the use of blends can be
1 interesting to modulate its properties, achieving suit-
Department of Food Engineering, School of Food
Engineering, University of Campinas (UNICAMP), able features such as reduction of pore size and solubility,
Campinas, SP 13083-862, Brazil besides the strengthening or weakening of the gel network

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according to the application. In this context, the combi- produced. The solutions were prepared by heating water up
nation of pectin with corn starch to produce hydrogels can to 90 8C, followed by the addition of pectin and starch. The
result in self-sustaining structures with better retention and mixtures were kept in this temperature for 30 min, at nat-
protection of bioactive compounds. The association of ural pH (* 7), for corn starch gelatinization. Solutions
hydrocolloids with starch may promote the formation of were submitted to external gelation in 150 mM CaCl2
macromolecular interactions, which has shown improved solution, in order to produce macrogels, macrobeads, and
functional characteristics. This association presents microparticles.
advantages of being effective and safe by employing native For macrogels production, the biopolymeric solutions
starch, therefore, free from the application of questionable were put into dialyses membranes (SnakeSkin Dialysis
chemicals (Zhang et al. 2018). Some papers have investi- Tubing, 3500 molecular weight cut-off, Pierce, Rockford,
gated the incorporation of starch into the pectin network IL, USA) in contact with a calcium chloride solution
and observed higher encapsulation efficiency of Lacto- (150 mM) for 7 days for posterior mechanical properties,
bacillus plantarum and greater resistance to digestive fluids microstructure, and water holding capacity (WHC)
when compared to pure pectin gel (Dafe et al. 2017). Also, evaluation.
high amylose starch and pectin hydrogels have been For the macrobeads, anthocyanin 0.05% (w/w) was
developed for controlled delivery systems, with higher added in the biopolymeric solutions as a model bioactive
amounts of pectin related to the formation of stronger compound. In this case, solutions were dropped (* 1 cm
networks (Soares et al. 2013). These results indicate the height), using a 2-mm inner diameter tube coupled with a
potential to investigate further properties of these systems peristaltic pump (Masterflex, model 7518-00, USA), into
for their application in encapsulation systems to achieve calcium chloride (CaCl2) solution (150 mM) and main-
bioactive protection and controlled delivery. tained in contact with CaCl2 for 5 min (curing time). The
This work aimed to produce pectin-starch gels through amount of gelling agent used was ten times the quantity of
different process preparation (dialysis, dripping and dripped solution, and after curing, the particles were
atomization) as encapsulating structures of bioactive com- washed with deionized water to remove salt excess. Such
pounds and investigate how starch concentration and polymer macrobeads were tested regarding their encapsulation
content impact hydrogels macro and microstructure. Antho- efficiency and process yield.
cyanin was added to the particles as a model compound and Finally, to produce microparticles all formulations also
microparticles was added to grape nectar in order to study the containing anthocyanin 0.05% (w/w) were passed through
effects of microparticle addition on rheological properties. an atomizer nozzle with 0.7 mm diameter (Labmaq, Brazil)
under compressed air (p = 1.0 bar) using a peristaltic pump
(Masterflex, model 7518-00, USA). The distance between
Materials and methods the atomizer and the gelling bath (CaCl2) was set at 30 cm.
The microparticles were maintained during 5 min in CaCl2
Materials solution for gelling. A sieve of 0.053 mm mesh diameter
was used to collect the microparticles, which were sub-
Low methoxyl pectin (DE 35%) was gently supplied by mitted to particle size distribution and optical microscopy
CPKelco (São Paulo, Brazil); Corn starch (21.33 ± 0.05% analysis. Rheological measurements of microparticles
amylose) was kindly donated by Ingredion (Mogi Guaçu, suspensions were also carried out to verify possible mod-
Brazil). Calcium chloride was purchased from Synth (Di- ifications in the grape nectar with microparticles addition.
adema, Brazil); Blackcurrant anthocyanin extract (purity of All systems were produced at least twice.
34.32%) was donated by Chr-Hansen (Valinhos, Brazil)
and grape nectar (Dia, Brazil) was purchased from a local Characterization of macrogels
market. The other chemicals were of analytical grade and
used without further purification. Mechanical properties

Preparation of biopolymeric solutions and hydrogels The macrogel samples were evaluated according to the
uniaxial compression test using a TA-XT Plus Texture
Pectin/starch gels were prepared in four different formu- Analyzer (Stable Micro Systems, UK). Macrogel cylinders
lations containing pectin (P) and starch (S) [F1: 1% P and with 2 cm diameter and height were subjected to uniaxial
1% S; F2: 0.5% P and 0.5% S; F3: 0.25% P and 0.75% S; compression measurements, up to 80% of their original
and F4: 0.75% P (w/w) and 0.25% S (w/w)]. To understand height using a cylindrical acrylic plate (80 mm of diame-
the effect of starch addition into the pectin network, a ter). A test velocity of 1 mm s-1 was set. The Hencky
control gel containing only 1.0% (w/w) pectin (F0) was stress (Eq. 1) and strain (Eq. 2) at the fracture were

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obtained from the first peak of the stress–strain curve. The quantified by the pH differential method with some mod-
Young’s modulus was obtained from the slope in the linear ifications (Lee et al. 2005). This method consists in mea-
range (up to 5% strain) (Eq. 3). At least five pieces of each suring the absorbance of samples (Spectrophotometer UV–
gel was measured. Vis; Bioespectro; Model SP 220; BRAZIL) in two pH’s
H ðt Þ (1.0 and 4.5) and two wavelengths (515 and 700 nm). The
rH ¼ F ðtÞ  ð1Þ anthocyanin amount was determined based on cyanidin-3-
H0 :A0
  rutinoside, the component present in higher amount in
H ðt Þ anthocyanin extract (Eq. 4).
eH ¼  ln ð2Þ
H0 mg DA:MM:DF:1000
rt C ¼ ð4Þ
E¼ ð3Þ l l:e
et
where DA is the difference on absorbance (A) at different
F(t) (N) and H(t) (m) correspond to the force and height wavelengths and pH:
at respectively time t (s); while A0 (m2) and H0 (m) are the
DA ¼ ðDA515  DA700 ÞpH1  ðDA515  DA700 ÞpH4:5
initial area and height of the sample, respectively.
where MM = molar mass of Cyanidin-3-Rutinoside
Water holding capacity (WHC) (595,53 g mol-1) (National Center for Biotechnology
Information, 2017), DF = dilution factor, 1000 = Conver-
Water holding capacity was measured according to the sion factor for from g to mg, l = Pathlengh (1 cm),
method described by Braga and co-authors (Braga et al. e = Molar Extinction Coefficient (28,840 L x mol-1-
2006) with some modifications. A cylindrical macrogel 9 cm-1) (Gouvêa et al. 2012).
(* 3 g) was put in Whatman # 1 filter paper (Whatman, The encapsulation efficiency was calculated as follow
UK) and centrifuged at 4000 g for 10 min at 22 8C. The (Eq. 5):
samples were weighed before and after centrifugation to  
100: ðC:V Þi ððC:V2 ÞÞ
determine WHC. Three replicates were performed for each %EE ¼ ðC:V1 Þ ð5Þ
macrogel sample. ðC:V Þi
ðC:V Þi = Initial mass of anthocyanin added in the paste
Scanning electron microscopy (g); ðC:V1 Þ = Anthocyanin mass lost in calcium chloride
(g); ðC:V2 Þ = Anthocyanin mass lost in washing water (g).
To evaluate the internal microstructure of the hydrogels,
scanning electron microscopy was performed. Macrogels Process yield
samples were fixed in glutaraldehyde (2.5%) prepared in
cacodylate buffer 0.1 M (pH 7.2), for 24 h. Subsequently, The yield of the dripping process was obtained by the
the samples were washed in cacodylate buffer 0.1 M and correlation between the mass of dripped biopolymeric
crio-fractured under liquid nitrogen. Dehydration of sam- solution and the mass of the produced macrobeads.
ples in ethanol series (30%, 50%, 70%, 90%) was con-
ducted, with the final step performed three times with Characterization of microparticles
100% ethanol. A critical point drying (Balzers Critical
Point Dryer CPD03) was carried out and the samples were Optical microscopy
adhered to aluminum stubs and coated with gold in a
Sputter Coater (Sputter Coater POLARON, SC7620, VG To analyze the morphology of the produced microparticles
Microtech, Uckfield, England). Images were captured by a a Scope A1 optical microscope (Carl Zeiss, Germany),
scanning electron microscope (LEO440i EDS6070 Cam- with a 1000 9 magnification was used. Samples were dyed
bridge, England), using acceleration of 10 kV. with iodine to visualize the corn starch granules in the gel
network.
Characterization of macrobeads
Particle size distribution
Encapsulation efficiency
Particle size distribution analysis was carried out for
The encapsulation efficiency (EE) was determined by the microparticles using a Mastersizer S (Malvern Instruments
quantification of anthocyanin losalong the whole process of Ltda, UK). For the analyses, particles were dispersed in
the particle formation. Thus, the amount of anthocyanin distilled water for the determination of the mean particle
present in calcium chloride solution and washing water was diameter D [3,2] and the polydispersity index (SPAN).

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Rheological measurements Such larger pores may also have affected the strain values
(Fig. 2b), considering a less cohesive structure formed
In order to study how the microparticles addition modify brittle gels (Fig. 3a, d), that fractured at lower strain values
characteristics of food products, rheological properties of (0.39 and 0.41 for F0 and F3 respectively). In this samples,
the grape nectar was measured with addition of different the maximum deformability of the network was easily
amount of microparticles (5–20% w/v). A stress-controlled achieved resulting in the rupture of the material (Zhang
rheometer (TA Instruments, AR1500ex, New Castle, DE, et al. 2005). The findings for pectin gels were the opposite
USA) equipped with a plate-plate geometry (d = 40 mm) of observed for gellan gels, in which the more porous
was used. Gap varied depending on the sample and it was structure presented greater deformability (Yamamoto and
always larger than the suspended particles. Flow curves of Cunha 2007). Such differences could be explained not only
pure nectar and nectar added of microparticles were eval- by the porosity and pore size but also by the different
uated, at 25 8C, in a shear rate of 0 and 300 s-1. All gelling mechanisms used in the present work (ionotropic
measurements were conducted in triplicate. gelation) and in the literature (acid gelation).
Moreover, the F0 and F3 exhibited lower stress at
Statistical analysis fracture (0.5 and 3.4 kPa respectively) (Fig. 2a) and Young
Modulus (1.26 and 3.03 kPa respectively) (Fig. 2c), which
The statistical treatment of the data was conducted using was associated with the formation of a non-dense and non-
Sisvar software (Ferreira 2011). The significant differences resistant gel network (Pires Vilela et al. 2011; Yamamoto
between the mean values were determined by the Tukey and Cunha 2007).
test, with 95% confidence level. In general, results indicated that starch addition
improved the pectin gel network decreasing the size of
pores (Fig. 3), and increasing WHC (Fig. 2d). Amylose
Results and discussion and amylopectin are the major starch components and they
are both composed by glucose residues (Alcázar-Alay et al.
Evaluation of the macrogels 2015; Miles et al. 1985; Takeo et al. 1973), resulting on a
net charge close to neutrality, which minimizes the possi-
To evaluate pectin/starch hydrogels characteristics, bility of electrostatic interactions. In addition, it was pos-
macrogels were prepared by membrane dialysis. The sible to observe starch remaining granules filling the pores
physical structure of these hydrogels can be observed in of pectin structure (red arrows) (Fig. 3). The increase in the
Fig. 1. These hydrogels were subjected to evaluation of WHC values (Fig. 2d) could be explained not only by the
their mechanical properties (Fig. 2a–c), WHC (Fig. 2d), larger pores but also by the structuring of pectin network.
and microstructure (Fig. 3). All formulations produced When pectin is in higher amounts ([ 0.25% P w/w), it may
self-sustained gels (Fig. 1); however, formulations F0 and uptake the water previously released by the starch during
F3 demonstrated strong syneresis (%WHC: 20.94 and retrogradation to structure its own network, resulting in a
15.55, respectively), while the other samples exhibited denser gel (Fig. 3b, c and e). In addition, it has been
lower release of water (Fig. 2d). The absence of syneresis reported that the presence of pectin associated with starch
after gel formation is related to a good stability of the gel involves the starch granules and cause interference in
structure (Yamamoto and Cunha 2007). For pectin-starch gelatinization, reducing swelling and syneresis (Zhang
blends at the same polymer content (F2; F3 and F4), the et al. 2018). Higher water absorption capacity of pectin-
lower amount of pectin caused a decrease on water uptake starch blends compared to starch formulations were also
(F3) (Fig. 2d). Similar result was reported for pectin/starch observed for film production (Da Róz et al. 2016). The
hydrogels, in which the reduced water entrapment was authors attributed this behavior to the presence of pectin’s
associated with a reduction in the ratio of pectin (anionic galacturonic acid hydroxyl, amide and carboxyl groups in
biopolymer), the responsible for trapping water in the the pectin structure that interact with water.
junction zones through the gelation process (Dafe et al. Concentration, pore size, and polymers structure can
2017; Da Róz et al. 2016), condition in which the hydroxyl also influence the water holding capacity of gels (Mo-
groups of hydrocolloid structure, alow more water inter- hammadian and Madadlou 2016). Results indicated that
action through hydrogen bonds (Nawab et al. 2014). Zhang different WHC was found for different total biopolymer
et al. (2018), attributed the effect of pectin on syneresis content (F1 presented 55.2 and F2 38.8% WHC) (Fig. 2d).
reduction to a viscosity increase. Lower biopolymer concentration (F2) is directly related to
The lower water retention could be associated with a smaller amount of molecules available to bind water,
structure containing larger pores, represented by pure which results in lower water retention in the gel structure
pectin gel (F0) and F3 (0.25% P and 0.75% S) (Fig. 3a, d). (lower WHC). Moreover, comparing the mechanical

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Fig. 1 Macrogels of pectin (P)/starch (S) produced in membranes by saline diffusion. a F0: 1% P, b F1: 1% P and 1% S, c F2: 0.5% P and 0.5%
S, d F3: 0.25% P and 0.75% S and e F4: 0.75% P (w/w) and 0.25% S (w/w)

a 0.8 b 15 c 100 d
Stress at Rupture (KPa)

25 b a a

Young Modulus (KPa)

b
Strain at Rupture (-)

a 80
20 0.6
b 10 a

WHC (%)
15
e b 60 b
c 0.4 d b
10 40
5 c c c
d 0.2 a c
5 20
a
0 0.0 0 0
F0 F1 F2 F3 F4 F0 F1 F2 F3 F4 F0 F1 F2 F3 F4 F0 F1 F2 F3 F4
Formulaons Formulaons Formulaons Formulaons

Fig. 2 a Stress at fracture, b strain at fracture, c Young’s modulus 0.25% P and 0.75% S; F4: 0.75% P (w/w) and 0.25% S (w/w)).
and d water holding capacity (WHC) of pectin (P)/starch (S) macro- Lowercase letters show differences (p \ 0.05) between the
gels (F0: 1% P; F1: 1% P and 1% S; F2: 0.5% P and 0.5% S; F3: formulations

properties of F1 and F2 (Fig. 2a–c), the results showed that increase of pectin content pointed to the strengthening of
when the pectin/starch ratio is maintained, and the total the structures as previously observed (Soares et al. 2013).
biopolymer concentration is increased (F1), an increase in The strain at fracture was not affected by different
the Stress at Rupture (F1: 20.95 and F2: 9.22 kPa) (Fig. 2a) biopolymers concentration (F1 and F2) (Fig. 2b) indicating
and Young Modulus (F1: 12.08 and F2: 3,49 kPa) (Fig. 2c) it was mainly influenced by how linkages were established
is observed, without affecting the Strain at Fracture and the organization of the network instead of the number
(Fig. 2b). According SEM images, a more packed and of linkages, as observed for the Young Modulus.
cohesive structure could be observed in this case (Fig. 3b).
Stress at Fracture is generally related to the gel hardness Characterization of the macrobeads
which is influenced by the strength of the chains and the
size of the pores (Braga et al. 2006; Zhang et al. 2005). The Encapsulation efficiency (EE) determines the incorporated
higher amount of biopolymer in the network results in bioactive amount inside particles in comparison with the
more molecules available to interact mainly by ionic bonds initial content added in the biopolymeric solution (Okuro
between pectin and calcium ions, which resulted in a more et al. 2015). Depending on the process, chosen polymers,
packed network and more structured gel. The Young type of incorporated bioactive and interactions between the
Modulus, on the other hand, is related to the firmness and active and the network, the structure can result in higher or
elastic properties of the materials at low deformations, and smaller encapsulation efficiency.
it can be associated with the linkage of biopolymers (Braga All formulations presented high EE ([ 75%) and starch
et al. 2006). Thus, the more polymer is added, the more addition did not increase the pectin ability to entrap
junction zones are formed and the higher is the firmness of anthocyanin into the core of particles (Fig. 4a). Moreover,
the gels (F1). Among pectin-starch blend formulations, different total biopolymer content (F1 and F2) did not show
higher pectin concentrations (F1 and F4) increased the significant differences (p [ 0.05), entrapping the same
elasticity modulus (12.08 and 5.78 kPa respectively) amount of anthocyanin in their structures (Fig. 4a). Previ-
(Fig. 2c) and stress at rupture (20.95 and 12.15 kPa ous work has also shown that the encapsulation efficiency
respectively) (Fig. 2a), regardless polymer content. The has not been affected by polymer ratio and drug

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a F0 (1%P) b F1 (1%P+1%S)

c F2 (0.5%P+0.5%S) d F3 (0.25%P+0.75%S)

e F4 (0.75%P+0.25%S)

Fig. 3 Scanning electron microscopies for macrogels formulations. a F0: 1% P; b F1: 1% P and 1% S; c F2: 0.5% P and 0.5% S; d F3: 0.25% P
and 0.75% S and e F4: 0.75% P and 0.25% S, at 2500 9 of magnification. The red arrows in the pictures indicate remaining starch granules

concentration for high amylose starch/pectin blends loaded production of macrobeads was directly related to water
with diclofenac (Soares et al. 2013). retention and strength of the gel network.
Concerning the yield, results showed that all formula-
tions presented yield higher than 60% (Fig. 4b). The Characterization of the microparticles
sample with the smallest amount of pectin (F3) produced
fewer mass of particles (61.54%) (smallest yield), probably The most compact and dense microstructure (Fig. 3b)
because pectin is the main responsible to structure the gel found among all formulations studied (F1) was the only
network. Besides, such formulation presented lower WHC sample able to form particles through atomization process,
(15.66% WHC) (Fig. 2d) and smallest stress at rupture showing the importance of polymer content and the process
(3.47 kPa) (Fig. 2a), indicating that the process yield in the used in particle formation. In this way, the microparticles
were characterized according to particle size distribution

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Fig. 4 a Encapsulation a 100 a b 100 a

ab b a a a
efficiency and b yield for bc c
macrobeads of pectin (P)/starch 80 80 b
(S) formulations (F0: 1% P; F1:

Yield (%)
EE (%)
1% P and 1% S; F2: 0.5% P and
60 60
0.5% S; F3: 0.25% P and 0.75% 40 40
S; F4: 0.75% P and 0.25% S).
Lowercase letters show 20 20
differences (p \ 0.05) between 0 0
the formulations F0 F1 F2 F3 F4 F0 F1 F2 F3 F4
Formulaons Formulaons

and morphology. Rheological behavior was also evaluated atomization using varied pressure/flow rate conditions,
when the microparticles were added to grape nectar (GN), which also showed monomodal behavior (De Moura et al.
once modifications on the rheological characteristics can be 2018). The authors reported that better protection is
related to acceptance or rejection of the product by the achieved for larger particles; however, for microparticles
consumer (Herh et al. 2000). dispersion in food products, smaller sizes are desired.
According to the optical microscopy (Fig. 5a), the Figure 6 illustrates the rheological behavior of GN with
obtained microparticles (1% P and 1% S) presented an the addition of different concentrations of pectin-starch
irregular shape and a non-homogeneous network; with microparticles (0–20% w/v). None of the samples pre-
starch remaining granules (dyed with iodine) irregularly sented thixotropy (data not shown). Considering that the
dispersed into the hydrogel particles. Similarly, the intro- shear rate of chewing and swallowing comprises the range
duction of whey proteins and hydroxypropyl methylcellu- of 10–100 s-1 (Steffe 1966), apparent viscosity at 100 s-1
lose for reinforcement of alginate and pectin beads, was calculated for all suspensions (Fig. 6). Results showed
affected negatively the morphology (Belščak-Cvitanović that addition of 5% of microparticles resulted in a slight
et al. 2016). The authors reported highest roundness for reduction on apparent viscosity, maintaining the pseudo-
pectin particles, while the introduction of other carrier plastic behavior of the grape nectar. Such behavior is the
materials and the use of binary mixtures reduced the result of particles alignment in the fluid shear field. Parti-
roundness of pectin microbeads. Although microparticles cles are organized into layers and offer less resistance
containing only pectin were not formed due to the low (lower viscosity) to flow (Chen et al. 2010). Furthermore,
biopolymer concentration, in the present work, the role of only the flow curves of the pure nectar and the nectar added
the starch reinforcing the encapsulation system was with 5% of particles presented a good fit for the shear
evidenced. thinning model (data not shown), with correlation index
The particle size distribution analysis (Fig. 5b) showed a (R2) higher than 0.99. Suspensions containing 10% or more
D3,2 of 65.80 lm ± lm ± 5.40 and a Span of particles showed an increase of apparent viscosity, which is
2.56 ± 0.09. Mean droplet diameters ranging from 77 to associated with the increased particle–particle interaction
275 lm were reported for pectin microparticles by (Brown and Jaeger 2014; Chen et al. 2010), due to the

a b 5

4
% Volume

0
1 10 100 1000 10000
Size (µm)

Fig. 5 Optical microscopy a and particle size distribution b of pectin (P)/starch (S) microparticles produced with 1% S (w/w) and 1% P (w/w),
containing anthocyanin. The blue-black complex indicates the presence of starch granules, dyed with iodine

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Fig. 6 Flow curves of

1.8
microparticles (F1: 1% Pectin
and 1% Starch) added in 1.6
different concentrations
(5–20%) in grape nectar (GN). 1.4

Shear Stress [Pa.s]

Lowercase letters indicate
1.2
significant difference (p \ 0.05)
in the apparent viscosity (gap) 1
between the formulations, at
100 s-1 0.8

0.6

0.4

0.2

0
0 50 100 150 200 250 300 350
Shear rate [s-1]

increased number of particles in suspension, as well as Acknowledgements The authors would like to thank Coordenação
swelling of the starch contained in particles. For these de Aperfeiçoamento de Pessoal de Nı́vel Superior (CAPES) (DEA/
FEA/CAPES-AUXPE 0535/2018) for the financial support and fel-
samples, two distinct behaviors were noted: below 100 s-1 lowships; the companies CPKelco, Chr Hansen and Ingredion for
the suspension showed a reduction of viscosity with sample donation and the access to equipment and assistance provided
increasing shear rate, which is typical of a pseudoplastic by the Laboratory of Process Engineering, Faculty of Food Engi-
fluid, while above 100 s-1 a shear thickening behavior was neering at the University of Campinas co-funded by FAPESP (2007/
58017-5; EMU2009/54137-1; 2004/08517-3).
observed. Thus, flow model could not be adjusted in these
cases.
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