International Journal of Biological Macromolecules 129 (2019) 665–671

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International Journal of Biological Macromolecules

journal homepage: http://www.elsevier.com/locate/ijbiomac

Use of guar gum, gum arabic, pectin, beta-glucan and inulin for
microencapsulation of anthocyanins from chokeberry
Ewelina Pieczykolan, Marcin Andrzej Kurek ⁎
Department of Technique and Food Development, Warsaw University of Life Sciences, Nowoursynowska 159c, 02-776 Warsaw, Poland

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

Article history: The aim of this study was to use micro-encapsulation technology to create microcapsules containing anthocya-
Received 5 November 2018 nins from chokeberry with guar gum, gum arabic, pectin, β-glucan and inulin as wall material. Aqueous extracts
Received in revised form 1 February 2019 from chokeberry fruit were enclosed and spray dried using maltodextrin as a coating material with the addition
Accepted 12 February 2019
of guar gum, gum arabic, pectin, beta-glucan, and inulin respectively. Physical properties of microcapsules were
Available online 13 February 2019
tested. The preparations also determined the total content of anthocyanins and vitamin C on the day of prepara-
Keywords:
tion and after 7 days of storage. In the executed research, the highest moisture content for gum arabic capsules
Dietary fiber was observed. The most different parameters of color were observed for capsules with beta-glucan. The biggest
Chokeberry particles were observed for gum arabic and the smallest for guar gum. The differences were also noticed in chem-
Microencapsulation ical assays. The highest content of anthocyanins on the day of drying and after 7 days of storage was noticed for
Anthocyanins beta-glucan samples whereas the lowest content was observed for gum arabic samples. In case of vitamin C con-
tent, the sample, which stood out particularly, was pectin sample. The main conclusion is that the micro-
encapsulation is an effective method to maintain the stability of sensitive compounds such as anthocyanins,
but also ascorbic acid.
© 2019 Elsevier B.V. All rights reserved.

1. Introduction
Today's food technology faces a great challenge. The previous
achievements of specialists in this field have allowed developing
many technologically advantageous solutions. Functional food is a
definite trend in the food industry. Nowadays, consumer requires
not only an easy to prepare or even a finished product but also one
that will have a positive effect on health. To increase the pro-health
potential of food products, technologists decided not only to enrich
food with vitamins and minerals but also with bioactive compounds.
The ideal situation is when a bioactive compound of plant origin with
extensive pro-health properties can also play technological func-
tions in the product.
One of the groups of bioactive compounds with such features are an-
thocyanins [1]. They are pigments of vegetable origin with a color de-
pendent on the pH, from red to blue, present in the skin, and often
also the flesh of some vegetables and fruits. Anthocyanins belong to
the group of flavonoids - a very extensive group of plant substances -
polyphenols. The basic units of the anthocyanin molecule are
anthocyanidins that consist of an aromatic ring bonded to an oxygen-
containing heterocyclic ring, which is also bound to the third aromatic
⁎ Corresponding author.
E-mail address: marcin_kurek@sggw.pl (M.A. Kurek).
ring. Anthocyanidins associated with the sugar residue form a glycoside,
which is anthocyanin [2,13,14]. There is a vast amount of anthocyanins
in nature. The main differences between them are the number of hy-
droxyl groups, the type and number of bound sugars, the aliphatic or ar-
omatic carboxylates bound to the sugar in the molecule, and the
position of these bonds. Excellent source of anthocyanins is chokeberry
fruits (Aronia menalocarpa). They contain approximately 1500 to
4400 mg/kg of these compounds in total. This amount depends mainly
on the variety and method of cultivation. The most common anthocya-
nins found in chokeberry are cyanidin-3-galactoside and cyanidin-3-
arabinoside [1]. As antioxidants, anthocyanins are very chemically un-
stable compounds. The factors such as temperature, light, oxygen avail-
ability, pH, chemical structure, concentration, solvents, presence of
enzymes, flavonoids, proteins, and metal ions are particularly unfavor-
able for the stability of these compounds [2,16,17].
Anthocyanins are one of the most important antioxidants supplied
with food. They have a very positive effect on many body functions.
They have anti-inflammatory effects, which may prevent the occur-
rence of some chronic diseases [6]. They also have a beneficial effect
on glycemic control and lipid regulation [7,8]. Thanks to their antioxida-
tive action, they inhibit free radical reactions, positively affecting the
condition of blood vessels, inhibiting the development of cardiovascular
diseases and others [9]. In addition, they improve the functioning of the
eye and protect the nervous system [10].

https://doi.org/10.1016/j.ijbiomac.2019.02.073
0141-8130/© 2019 Elsevier B.V. All rights reserved.
666 E. Pieczykolan, M.A. Kurek / International Journal of Biological Macromolecules 129 (2019) 665–671
Other compounds that might be functional food additives are solu-
ble fiber fractions, mainly hydrocolloids and oligosaccharides. Among
the ones that are commonly added to foods, we can mention substances
in a natural form, e.g., inulin, beta-glucan, locust bean gum, but also nat-
ural substances modified as carrageen, alginates, methylated and
amidated pectins, modified starches. As a fiber, they positively affect
the intestine status. By binding water in the digestive tract, they provide
a feeling of fullness. They feed the intestinal microflora. In addition, they
have the ability to bind cholesterol and bile acids in the intestine, and
thus increase their excretion. They lower the level of glucose in the
blood on an empty stomach and after a meal [5].
What is more, soluble fiber fractions play critical technological
functions in food. They are used as stabilizers, thickeners, fillers or
emulsifiers. They are an important texture forming element. Often
the product they substitute fat and even sugar in food products.
This allows the creation of a functional product with a reduced en-
ergy value. In addition, aqueous solutions of hydrocolloids and oligo-
saccharides are used as a coating material in microencapsulation
technology.
The use of various coating materials in microencapsulation technol-
ogy allows obtaining different physicochemical properties such as
water activity, moisture content, shelf-life, and hygroscopicity. These
parameters depend on the structure and properties of each coating ma-
terial [36]. The most commonly used coating material is maltodextrin,
because it is cheap, has good solubility, low viscosity, and high microen-
capsulation efficiency. In addition, maltodextrins are characterized by a
mild taste, and their solutions are colorless. Depending on the degree of
hydrolysis, maltodextrins with different molecular weights are ob-
tained, which are varied in terms of the density of the coating around
the bioactive component that they close. Maltodextrins with degrees
of dextrose equivalence (DE) between 10 and 20 are used most com-
monly in the encapsulation of anthocyanins [27]. However, a number
of studies prove that the use of a combination of maltodextrin and hy-
drocolloid increases the efficiency of the process [24–26]. Microencap-
sulation allows the storage of sensitive bioactive compounds in a form
that slows down the degradation processes before they are used in the
product [34,35].
The microencapsulation technology is now an essential element of
food processing. It involves coating one substance with another [3,4].
Spraying is the most commonly used method. This process consists of
dissolving, emulsifying or dispersing the active ingredient in an aqueous
solution of the coating material and then spraying it in hot air. During
this process, a coating is formed on the surface of the droplets; the larger
particles of the coating substance remain while the smaller water mol-
ecules are evaporated. Spray dryers in the food industry typically spray
the emulsion with a high-pressure nozzle and operate with the co-
current flow of air and particles to ensure minimal particle overheating.
This is particularly important if the encapsulated substance is sensitive
to high temperature or volatile (as with aromas) [4].
The problem with anthocyanins is that they are unstable due to fac-
tors like light and oxygen or air. Because of that, there is a constant need
to preserve the extract from various plants rich in anthocyanins using
methods like microencapsulation [15]. It was proved that the microen-
capsulation process could maintain the bioactive compounds' level even
if slightly changed relative to the extract [34]. Up to our best knowledge,
there is no a complex study which describes the application of various
dietary fibers as coating materials for microencapsulation of Aronia
melanocarpa extract. Therefore, the aim of the study was to use micro-
encapsulation technology to create a dried chokeberry coated with die-
tary fiber. Aqueous extracts from chokeberry fruit were encapsulated
and spray dried using maltodextrin as a coating material with the addi-
tion of guar gum, gum arabic, pectin, beta-glucan, and inulin. Microcap-
sules were tested for bulk density, moisture content, hydroscopicity,
water solubility, particle size, and color. The preparations also deter-
mined the total content of anthocyanins and vitamin C on the day of
preparation and after 7 days of storage.
2. Materials and methods
2.1. Material
The materials for the tests were freeze-dried fruits of black choke-
berry Aronia melanocarpa provided by the local supplier. The following
hydrocolloid preparations were used to prepare solutions for coating
materials: maltodextrin (MD with DE 18–20), gum arabic (GA), inulin
(IN) pectin (PEC), and guar gum (GG) (Agnex, Poland). Beta-glucan
from barley beta-glucan preparation was extracted in the study de-
scribed by Kurek et al. [18].
2.2. Methods
2.2.1. Extraction and preparation of microcapsules
In order to obtain anthocyanins extract, freeze-dried chokeberry
fruits were ground in a laboratory mill and sifted to a maximum size
of 0.5 mm. Then 30 g of dried material was placed in a dark bottle
with 100 ml of an acetone-water mixture (80–20). The suspension
was then placed in an ultrasonic bath (Tovatech E100H, Elma, USA) in
ambient temperature for 15 min ultrasonication. Then the bottles
were left for sedimentation for 1 h. The suspension was then filtered
through a 0.45 μm filter to the separatory funnel, and the same volume
of petroleum ether was added and shaked for 5 min. After layer separa-
tion, the lower one was collected and evaporated using rotary evapora-
tor up to the non-recognizable smell of acetone and 15° Brix extract
concentration.
Solutions of coating materials were prepared by dissolving MD in an
amount of 74 g and 6 g of hydrocolloids and dietary fibers (GA, IN, PEC,
GG, and BG) in distilled water in an amount of 200 ml to obtain 40% of
solids in solution. The mixtures were heated to 60 °C and stirred on a
magnetic stirrer until hydration of the polysaccharides. In order to pre-
pare the mixture for drying, 40 g of the chokeberry extract was succes-
sively combined with 120 g of the solution of each coating material. The
whole solution was homogenized for 3 min at 8000 rpm using the
Ultraturrax IKA homogenizer. The obtained homogenates were placed
successively in a Buchi B-290 spray dryer. The drying process was
carried out at 140 °C, pump flow 25%, air flow 600 l/h. The finished mi-
crocapsules were placed in brown plastic tubes and sealed. The prepara-
tions were stored at −20 °C.
The resulting microcapsules were tested on the following day after
drying and after 7 days of drying stored in transparent tubes with con-
tact to light and oxygen at room temperature to examine the ability of
preservation of various wall materials.
2.2.2. Physical tests
The bulk density was determined first. Each of the prepared powders
was poured into a measuring cylinder successively; the volume was
read and then weighed. Bulk density was shown as a mass/volume
ratio [g/cm3].
Moisture content was measured using a RAD WAG MA 50 scales
dryer and expressed as a percentage.
Hygroscopicity was determined by weighing about 1 g of powder
into aluminum capsules and placing them in a container with satu-
rated sodium chloride (75% NaCl). Samples were placed in a desicca-
tor at 25 °C and weighed every 48 h until equilibrium was reached.
Hygroscopicity is expressed in 1 g adsorbed moisture per 100 g dry
substance (g/100 g). The equation [38]:
HG ¼ ðΔm=ðM þ M i ÞÞ=ð1 þ Δm=M Þ ð1Þ
where Δm (g) - increase in powder mass after equilibrium, M (g) -
initial mass of powder, Mi (g) - mass of free water powder before ex-
posure to moist air.
The water solubility of the microcapsules was determined according
to the following method. About 1 g of powder and 100 ml of distilled
 E. Pieczykolan, M.A. Kurek / International Journal of Biological Macromolecules 129 (2019) 665–671
water were placed in a beaker. The beaker was set on a magnetic
stirrer and mixed for 5 min. The solution was then centrifuged
(3000 g, 15 min) in a Hettich Universal R. centrifuge. Subsequently,
25 ml of the supernatant was transferred to a 50 ml beaker and
dried at 105 °C for 24 h in an oven drier. The solubility (%) was cal-
culated from the weight difference before and after drying using
the equation:
Solubility ¼ P a −P b =0:25  100
where Pa (g) - mass of the beaker and samples after drying, Pb (g) -
initial weight of the weighed beaker.
The color of the powders were measured using a Minolta CR-400
colorimeter (Konica Minolta Inc., Japan) using the CIELab measurement
system (measuring area ø = 8 mm and observer 2°, light source D65). L*
parameters were determined (the brightness of L* values ranges from 0
(black) to 100 (white)), a* (the value on the red axis - plus and green
values - minus values) and b* (the value on the yellow axis - plus values
and blue axis - minus values). In addition, the overall difference in ΔE
was calculated.
The particle size distribution and dispersibility were determined
using a Morphologi® G3SE apparatus (Malvern Instruments Ltd.,
Malvern, UK) equipped with a dispersion unit for dry samples. The par-
ticle size distribution was calculated as the relative volume of particles
in the size bands shown as size distribution curves (Malvern Microsoft
ware v. 5.40, Malvern Instruments Ltd.). The particle size distribution
parameters included the largest particle size (D [v, 0.9]), mean particle
volume (D [v, 0.5]), and the smallest particle size (D [v, 0.1]). The poly-
dispersity index was estimated as follows: (D90-D10)/D50.
To perform SEM analysis, small amount of the samples were placed
on the surface of the double-sided tape attached to the stubs. Then the
samples were observed under vacuum using a scanning electron micro-
scope QUANTA 200.
To measure thermodynamic changes of powders differential scan-
ning calorimetry (DSC1, Mettler Toledo, USA) was used. Nitrogen flow
was used at the gas flow 30 ml/min. A sealed and empty aluminum
pan was accurately weighed and used as a reference. Approximately
10 mg of each powder was weighted and placed in DSC pan. The
hermetically sealed pan was heated from 25 °C to 250 °C at a rate of
10 °C/min. After the thermal analysis, phase transformation curve was
obtained and temperature of glass transition and II phase transition
were pointed.
2.2.3. Chemical tests
The prepared preparations determined the content of anthocyanins
and vitamin C one day after preparation and after 7 days of storage with
the access of light and air. TAC was determined by pH differentiation.
0.2 g of each sample was dissolved in 10 ml of distilled water in a volu-
metric flask, then homogenized to destroy the capsules. The absorbance
was measured at 510 nm and 700 nm. The designation was carried out
in three replications. The total amount of powder anthocyanin (TAC)
was calculated according to the following equations:
TAC ðmg=kgÞ : DA  Mw  Df  1000=ðMa  LÞ
DA ¼ ðA510−A700Þ pH 1:0−ðA510−A700Þ pH 4:0
With DA: difference in absorbance, Mw: molecular weight for
cyano-3-glucoside (449.2 g mol−1), Df: sample dilution rate, Ma -
molar absorptive for cyanide 3-glucoside (26,900 L mol−1 cm−1), and
L: cell diameter of the spectrophotometer (cm). The results are
expressed as mg of cyanide-3-glucoside equivalents per 100 g dry
weight of powder (mg/100 g).
The encapsulation efficiency was analyzed. For this purpose, two
values were compared - surface anthocyanins content (SAC) and total
anthocyanins content (TAC). To investigate SAC, the procedure
667
was the same as in the case of TAC determination, skipping the homog-
enization step. The yield was calculated as follows:
TAC−SAC
Efficency ¼  100% ð5Þ
TAC
The content of ascorbic acid in capsules was determined using high-
ð2Þ performance liquid chromatography. The sample preparation was as
follows: 500 mg of powder was weighed, and 2.5 ml of pH 3 0.01 M for-
mate buffer was poured. The samples were then homogenized (30s,
8000 rpm) and centrifuged in a centrifuge (10 min, 3000 rpm). The su-
pernatant was gathered into a syringe, and 0.45 μm syringe filter was
fed into a vial of autosampler. The samples were placed in the chro-
matograph and analyzed using Shimadzu (Kyoto, Japan) system,
consisting of a column oven (model CBM-20A), a UV–visible diode-
array detector (model SPD-M10), a degasser (model DGU 20A), and a
liquid chromatography pump (model LC-20AD). The column was C18
15 cm long. The conditions for ascorbic acid determination were 95%
of formate buffer (A) and 5% methanol (B) with isocratic flow
1 ml/min. The assay was carried out in three replications. The results
were elaborated with reference to the standard and expressed in mg/
100 g of powder.
2.3. Statistical analysis
The obtained results were analyzed using the Statistica 13.1 pro-
gram. A one-way analysis of variance ANOVA was applied.
3. Results and discussion
3.1. Bulk density
All microcapsules were statistically different in terms of density
(Table 1). The highest density was determined by IN capsules
(0.95 g/cm3) and the lowest capsules from GA (0.78 g/cm3). Powders
with IN, PEC, and GG were distinguished by density above 0.90 g/cm3.
The differences between the tests result from the relationship between
the bulk density and the molecular weight of the coating material. Ma-
terials with a lower mass are more difficult to fill spaces between mole-
cules, taking more space than particles of heavier materials packed into
smaller volumes. This results in a lower bulk density [19]. In addition,
there are differences in the value of this parameter depending on the
shape, size, and properties of the particle surface [22]. As the density
of water is higher than that of a dry powder, its content also affects
the bulk density [20]. The drying speed is also important for this param-
eter. The surface of the particle may retain the original shape by harden-
ing the capsule when the drying occurs quickly or shrinks when the
water contained inside evaporates as a result of the slow process. In
the latter case, after evaporation, the surface of the capsule becomes
concave, and thus creates space for packing smaller particles between
larger ones [32].
ð3Þ 3.2. Moisture content
ð4Þ Significant variation in moisture content was observed among the
tested samples (Table 1). The sample from GA was the one with the
highest water content (2.73%). In similar studies [12], at the same dry-
ing temperature (140 °C), the moisture content in capsules from GA
was twice as high (5.45%). However, the flow rate was different,
which significantly influences the degree of dehydration of the capsules
[19]. The lowest level was observed for BG sample (1.29%). These differ-
ences are affected by different water-binding capacity for individual hy-
drocolloids, which is determined by the number of hydrophilic groups
present in the wall material molecule [21]. Moisture content for the
other samples was on a nominally similar level (1.75–1.84%).
668 E. Pieczykolan, M.A. Kurek / International Journal of Biological Macromolecules 129 (2019) 665–671

Table 1
Results of the bulk density, moisture content, hygroscopicity, water solubility and microencapsulation efficiency of microcapsules (average ± standard deviation). Different letters mean
statistically significant differences at p ≤ 0.05.

Sample Bulk density Moisture content Hygroscopicity [g/100 Water Efficiency [%] Glass transition II phase transition
[g/cm3] [%] g] solubility (°C) (°C)

Maltodextrin + arabic gum 0.78 ± 0.001a 2.73 ± 0.003e 0.13 ± 0.0001a 90.46 ± 0.1a 78.61 ± 1.60c 69.65 ± 1.11c 165.87 ± 1.16c
Maltodextrin + inulin 0.95 ± 0.001e 1.75 ± 0.002c 0.14 ± 0.0002b 90.3 ± 0.1a 88.37 ± 1.97a 68.02 ± 1.14b 179.15 ± 1.59d
Maltodextrin + beta-glucan 0.89 ± 0.001b 1.29 ± 0.001a 0.16 ± 0.0002e 89.54 ± 0.1b 92.78 ± 3.83a;b 66.19 ± 1.32a 160.84 ± 1.84b
Maltodextrin + pectin 0.93 ± 0.001d 1.84 ± 0.002d 0.14 ± 0.0002c 90.38 ± 0.1a 91.85 ± 3.12a;b 67.54 ± 0.95b 149.92 ± 1.54a
Maltodextrin + guar gum 0.91 ± 0.001c 1.66 ± 0.002b 0.15 ± 0.0002d 90.7 ± 0.1c 92.98 ± 0.87b 66.22 ± 1.18a 161.67 ± 1.45b

3.3. Hygroscopicity
Hygroscopicity is one of the most important parameters for deter-
mining the stability of powders. It is important that the use of a mixture
of maltodextrin and hydrocolloid as a coating material increase the hy-
groscopicity of the powder in relation to the use of only maltodextrin
[36]. This parameter also varied all samples statistically (Table 1). The
highest hygroscopicity was shown by the sample with BG
(0.16 g/100 g). This may mean greater dehydration of the hydrocolloid
during drying than the other samples, but also suggests the worst shelf-
life of the powder. The lowest value of this parameter was distinguished
by the sample from GA (0.13 g/100 g), so it can be concluded that this
powder will have the longest shelf-life. In other studies [12], it was
noted that the hygroscopicity of the capsules is much higher at the
same drying temperature (17.75 g/100 g). This may be due to the differ-
ent ratio of the used coating material. Differences in hygroscopicity of
different materials result from varied chemical structure and different
reactions with moisture present in the environment [21].
3.4. Water solubility
Powders with GA, IN, and PEC were not statistically different in
terms of solubility (Table 1). However, a significant difference was
noted for the trials with BG (89.54%) and GG (90.7%). An important fac-
tor for solubility is the particle size. The smaller the particles, the greater
the solubility of the powder [22]. On the other hand, there are studies
[36,37] that show the ability to form agglomerates, increasing the
water solubility of the powder. This is directly related to the water con-
tent of the capsule. The less water in the coating, the harder it is and the
less it is able to dissolve. However, this direct relationship has not been
found in this study.
3.5. Efficiency of microencapsulation
The microencapsulation efficiency among different coating mate-
rials was partially varied (Table 1). The lowest efficiency was obtained
with capsules coated by GA (78.61%), while the highest with capsules
were coated by GG (92.98%). Interestingly, the lowest efficiency was
achieved for the combination of materials most commonly used in en-
capsulation, for which the high efficiency of encapsulation has been
proven many times [24–26]. IN capsules were statistically different
from other samples, and for them, the efficiency was 88.37%. A similar
result was obtained by Robert et al. [11] where the efficiency of
microencapsulation of gallic acid coated in IN was 83%. The same orders
of magnitude were obtained by Mahdavi et al. [24], indicating at the
same time that an essential factor in the efficiency of encapsulation is
the ratio of the content of core to the wall material. They showed that
the most efficient ratio of core/wall material is 25%. A similar proportion
was used in this study. However, other researchers [28] found that the
efficiency of encapsulation increases with increasing the core/wall ma-
terial ratio.
3.6. Color measurement
Not all tested powders differed in terms of brightness (Table 2). No
statistically significant differences in this parameter were noted for
powders with GA and PEC. The darkest turned out to be capsules from
BG (L * = 71.64). The tone of the red color was different for all samples.
The most red was the powder with the addition of BG (a * = 12.03), the
least was with the addition of GG (a * = 9.04), which may indicate the
best effect of encapsulation in the case of GG [22]. The same trend was
observed for the yellow color. The overall difference in color turned
out to be statistically insignificant for GA and GG samples as well as
for GG and PEC. However, the samples from IN (ΔE = 74.72) and BG
(ΔE = 72.84) were significantly different. According to Silva et al.
[12], the use of GA as a carrier increases the ΔE value of the powder rel-
ative to the maltodextrin carrier. In addition, the differences in the color
of the powders depend on the type of coating material used; there is a
relationship between the percentage of coating material and the bright-
ness of the powder [31].
3.7. Particle size and PDI
The particle size statistically differentiated all samples (Table 3). The
highest mean particle size was recorded for capsules with the addition
of GA, which was N2–3 times higher than in the other samples (53.09
μm). For this powder also, the broadest range of particle sizes was
found (D10 = 8.31 μm, D 90 = 123.16 μm). Tonon et al. [19] found
that smaller particles can be located between larger ones, thus taking
less space. This phenomenon was associated with a high bulk density.
In this study, we observed an inverse relationship. With significant dif-
ferences in particle size, the lowest bulk density was found for GA. It can
be concluded that smaller particles do not locate between larger ones,
and the space between them remains empty. The smallest medium-
sized particles were characterized by GG capsules (16.29 μm). In
terms of parameters D10, D50, and D90, all the tests were significantly

Table 2
Results of the color measurement of microcapsules (average ± standard deviation). Different letters mean statistically significant differences at p ≤ 0.05.

Sample L* a* b* E*
a c b
Maltodextrin + arabic gum 74.01 ± 0.01 11.2 ± 0.03 4.92 ± 0.02 75.01 ± 0.01a
Maltodextrin + inulin 73.75 ± 0.05c 10.91 ± 0.06b 4.99 ± 0.01c 74.72 ± 0.05d
Maltodextrin + beta-glucan 71.64 ± 0.01b 12.03 ± 0.03e 5.39 ± 0.01e 72.84 ± 0c
Maltodextrin + pectin 74.05 ± 0.03a 11.75 ± 0.02d 5.23 ± 0.01d 75.16 ± 0.03b
Maltodextrin + guar gum 74.4 ± 0.1d 9.04 ± 0.02a 4.43 ± 0.02a 75.08 ± 0.1ab
 E. Pieczykolan, M.A. Kurek / International Journal of Biological Macromolecules 129 (2019) 665–671 669

Table 3
Results of the particle size measurement of microcapsules (average ± standard deviation). Different letters mean statistically significant differences at p ≤ 0.05.

Sample Particle size [μm] D10 [μm] D50 [μm] D90 [μm] PDI

Maltodextrin + arabic gum 53.09 ± 0.06e 8.31 ± 0.01d 24.13 ± 0.03e 123.16 ± 0.14e 4.75 ± 0.01e
Maltodextrin + inulin 17.66 ± 0.02c 7.43 ± 0.01c 15.96 ± 0.02b 30.57 ± 0.03c 1.45 ± 0c
Maltodextrin + beta-glucan 25.61 ± 0.03d 9.56 ± 0.01e 23.02 ± 0.03d 42.83 ± 0.05d 1.44 ± 0b
Maltodextrin + pectin 17.35 ± 0.02b 7.34 ± 0.01b 16.29 ± 0.02c 29.47 ± 0.03b 1.36 ± 0a
Maltodextrin + guar gum 16.29 ± 0.02a 6.73 ± 0.01a 13.92 ± 0.02a 27.83 ± 0.03a 1.51 ± 0.01d

different from each other. The highest median was observed for GA
(24.13 um), while the lowest for GG (13.92 um). The size of the particle
is affected by the polymeric structure of the coating material. The
shorter the polymer chain, the smaller the particle size [19].
The dispersion parameter also varied in all samples. It was 4 times
higher for the GA sample (4.75) than for the others. The lowest value
of this parameter was characterized by the PEC sample (1.36). There-
fore, it can be concluded that the GA powder forms particles of different
mass, at the same time, they do not easily form agglomerates. These fea-
tures partially favor the use of the powder, because different particle
sizes cause unequal dissolution of the powder and pigment release
and, at the same time, the absence of caking facilitates dissolution.
3.8. Anthocyanins and ascorbic acid content
In the case of total anthocyanin content, 1 day after drying did not
differ between the samples from IN and PEC (Table 4). The other cap-
sules varied this parameter. The highest levels of anthocyanins were
characterized by BG capsules (3055.65 mg/100 g), while the lowest cap-
sules were from GA (1940.22 mg/100 g). It can, therefore, be concluded
that β-glucan has the ability to close the extract with high efficiency. Ac-
cording to Tonon et al. [19], the high solubility of the coating material al-
lows the formation of a hollow capsule where the extract is entrapped
in the crust. However, this relationship was not confirmed in this
study because the BG powder had the lowest solubility value of all coat-
ing materials tested. However, most often, GA was used as a coating ma-
terial due to its high solubility, it did not distinguish positively with this
parameter while, at the same time, with the lowest content of anthocy-
anins in powder.
Comparing the content of anthocyanins in capsules powders and ex-
tracts, it can be seen that the drying process caused a very large loss of
anthocyanins. At the same time, it was found that factors such as storage
with access to light and air did not cause significant degradation of an-
thocyanins in the case of capsules with IN and GG. This proves that
the extract of chokeberry is efficiently coated by these polymers, and
it has a positive effect on anthocyanins. Coating materials play the role
of a physical barrier against the degrading agents of these colorants
[23]. Tonon et al. [19] concluded that the degradation of anthocyanins
occurs on the surface of the capsule, and the entrapped material is ade-
quately protected against the transfer of oxygen through the density of
the matrix and the distance from the destructive factor. Studies have re-
ported [28] that intermolecular connections between polysaccharide
polymers and polyphenol compounds result in stable microparticles,
and thus, such powders can be stored for a long time without significant
degradation of anthocyanins. Villacrez et al. [30] found that the content
of anthocyanins in the connections with the coating material did not de-
crease during storage despite the destruction of the capsule. At the same
time, Mirhojati et al. [31] have verified that storage of capsules at room
temperature significantly shortens the half-life of anthocyanins in cap-
sules compared to storage at refrigeration temperatures. However,
Hongmei and Meng [33] confirmed the gradual reduction of the content
of encapsulated anthocyanins with increasing temperature.
The total ascorbic acid content differentiated all samples, only the
GA and GG samples did not differ significantly (Table 4). For these two
samples, the level of ascorbic acid on day 1 after drying was the lowest
(GA 5.05, GG 5.02). The highest one was observed for PEC (12.19). This
may indicate a protective effect of pectin in relation to vitamin C during
the drying process. In all statistically examined capsules, significant deg-
radation of vitamin C was observed during storage. After seven days, the
ascorbic acid level was significantly different in all samples. The highest
percentage degradation was observed for IN capsules (approx. 47%),
and the smallest for GG (approx. 8%). Therefore, it can be concluded
that among all coating materials tested, GG limits the degradation of an-
thocyanins during storage and exposure to adverse factors to the
greatest extent.
3.9. SEM
Analysis of images from the electron microscope revealed significant
differences in the appearance of the capsules among various coating
materials (Fig. 1). Differences in the image, depending on the hydrocol-
loid used for coating, are confirmed by other studies [28,29]. Capsules
coated with GA had a round shape. Their surface was smooth, but in
many places, it was concave. The size of the capsules varied. Similar re-
sults were observed by Mahdavi et al. [24], where the MD/GA capsules
were smooth but heterogeneous compacted into agglomerates to a
small extent and had a larger size and were better distributed. These
are indications that the MD/GA combination is a good coating material
for water-soluble substances. Capsules with a IN as coating significantly
differ in appearance from the remaining samples. The particles were ag-
glomerated, irregular, with branches. Caking of powder particles with
inulin was also observed by Robert et al. [11]. These particles were
also relatively small - about 10 μm or smaller. On the one hand, the
small size of the particles facilitates dissolving, but on the other hand,
this size and irregular shape of particles facilitates the formation of cak-
ing, which is not desirable. However, there are studies [29] that the

Table 4
Results of the ascorbic acid content and total content of anthocyanins measurement in microcapsules in 1 and 7 day of storage (average ± standard deviation) and percent of degradation
during storage. Different letters mean statistically significant differences at p ≤ 0.05 – a between the rows and A between the columns.

Ascorbic acid [mg/100 g] Total content of anthocyanins [mg/100 g]

Sample Day 1 Day 7 % of degradation Day 1 Day 7 % of degradation

Extract 73.64 ± 2.37 – – 15,150.00 ± 1.24 – –

Maltodextrin + arabic gum 5.05 ± 0.18aA 4.66 ± 0.22cA 7.72 1940.22 ± 45.04bB 1543.99 ± 4.39aA 20.42
Maltodextrin + inulin 6.26 ± 0.18bB 3.32 ± 0.31aA 46.96 2730.84 ± 160.51aA 2447.27 ± 198.08cA 10.38
Maltodextrin + beta-glucan 6.7 ± 0.29cB 5.61 ± 0.09dA 16.27 3055.65 ± 4.13dB 2871 ± 114.65eA 6.04
Maltodextrin + pectin 12.19 ± 0.32dB 7.71 ± 0.33eA 36.75 2853.81 ± 48.63aB 2653.27 ± 44.98dA 7.07
Maltodextrin + guar gum 5.02 ± 0aB 3.91 ± 0.01bA 22.11 2319.76 ± 79.49cA 2185.02 ± 95.34bA 5.81
670 E. Pieczykolan, M.A. Kurek / International Journal of Biological Macromolecules 129 (2019) 665–671
Fig. 1. The SEM images of the microcapsules with anthocyanins – MD GA (maltodextrin + arabic gum), MD IN (maltodextrin + inulin), MD BG (maltodextrin + beta-glucan), MD PEC
(maltodextrin + pectin), MD GG (maltodextrin + guar gum).
inulin coated capsules have the shape of smooth, regular balls. The au-
thors indicate that the final shape and surface of the capsules depend
not only on the coating material but also on the rate of water loss in
the spray drying process. The capsules from BG were quite varied.
Larger elements were round and concave or disc-shaped. The smaller
ones were irregular and agglomerated. At the same time, the samples
from BG were characterized by the lowest solubility in water. Particles
with PEC addition were small, round, and concave. They had a smooth
surface. Most of the capsules were of a similar size. The GG samples
were circular or oval shaped particles with a smooth surface. The size
was not much diverse. Most of the image was filled with very small par-
ticles, but capsules with a diameter of about 15 μm were clearly visible.
These capsules were also characterized by the highest solubility and en-
capsulation efficiency, which may explain the regularity of shape and
the lack of caking of powder particles.
3.10. Thermodynamic characteristics of particles (DSC)
The thermal transformation curves for all tested samples were sim-
ilar. Two phase transitions in similar temperature ranges were ob-
served. From the initial temperature (25 °C) to about 67 °C no thermal
activity of the microcapsules was observed. For the glass transition tem-
perature, no statistically significant differences were found for all tested
samples (Table 1). The highest temperature of this transformation char-
acterized the MD GA sample (69.65 ± 1.11) and was significantly differ-
ent from the others. The lowest temperature values were shown by MD
BG (66.19 ± 1.32) and MD GG (66.22 ± 1.18). Differences may have re-
sulted from the different molecular weight of the hydrocolloids used.
This means that the optimal temperature for storing powders for stabil-
ity depends on the coating material used.
The second phase transformation varied almost all the samples
(Table 1). Significantly the highest temperature of this parameter was
noticed for the MD IN sample (179.15 ± 1.59) and the lowest for MD
PEC (149.92 ± 1.54). This peak may be related to the partial loss of
water by the powders. This may mean that the IN sample most strongly
binds water and therefore a higher temperature to evaporate is needed.
4. Conclusions
Microencapsulation is an effective method to maintain the stability
of sensitive compounds such as anthocyanins and ascorbic acid. How-
ever, not all combinations of maltodextrin and hydrocolloids are equally
effective. The structure of the particles affects not only the bulk density
of the powders but also the solubility and facility to forming agglomer-
ates. GG was characterized by the highest efficiency of encapsulation.
The particles of this powder were the smallest, preferably distributed,
of uniform size and shape. These features directly influenced the highest
solubility of this preparation among all powders.
An interesting observation in this study was the protective effect of
coating materials on the degradation of anthocyanins and ascorbic
acid. BG proved to bind the largest amount of anthocyanins from all
the tested materials, while the most of ascorbic acid was bound by
PEC. It was noted that the degree of protection against degradation of
both anthocyanins and ascorbic acid during storage with exposure to
destructive factors varies depending on the coating material used. De-
spite the best technological properties of the powder with the addition
of GG, it did not distinguish itself in terms of inhibiting the degradation
of ascorbic acid during storage. However, relevant information is that
despite the relatively low degree of binding of anthocyanins in the cap-
sule compared to the remaining test powders, GG showed the lowest
percentage degradation of these compounds during storage.
Not many studies show the stability of encapsulated anthocyanins in
the finished product. It has been established so far that the degradation
of anthocyanins protected by capsules in a product with a high water
content occurs very quickly [34,35]. Therefore, it is worth finding a
more effective solution for maintaining the high stability of natural pig-
ments in food. Thanks to this, it will be possible to use them widely and
reduce the use of synthetic colorants.
Acknowledgments
This work was supported by The National Centre for Research and
Development project “Microencapsulation as the technique for increas-
ing the application of beta-glucan in the food industry [LIDER/25/0022/
L7/15/NCBR/2016].” Special acknowledgments for Małgorzata
Sobieralska BSc for helping in laboratory assays.
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