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Powder Technology 277 (2015) 89–96

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Powder Technology

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

Modeling and stability of polyphenol in spray-dried and freeze-dried


fruit encapsulates
Mónica J. Ramírez, Gloria I. Giraldo, Carlos E. Orrego ⁎
Instituto de Biotecnología y Agroindustria, Departamento de Física y Química, Universidad Nacional de Colombia Sede Manizales, Campus la Nubia Km 4 Via al Magdalena,
AA 127 Manizales, Colombia

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

Article history: Several studies have investigated freeze-drying and spray-drying encapsulation to address the effect of opera-
Received 9 October 2014 tional parameters on the physicochemical properties and preservation of the polyphenol content in fruit encap-
Received in revised form 10 February 2015 sulates. Using a specific fruit or vegetable pulp or extract, most of these studies have examined the search for
Accepted 27 February 2015
an appropriate wall. In this study, the effect of operational variables and the concentration of maltodextrin
Available online 6 March 2015
(MD) and gum arabic (AG) on the gallic acid (GA) content of spray- and freeze-dried encapsulates of a model
Keywords:
fruit juice (MFJ) was evaluated. Three encapsulant ratios (100% MD, 100% AG, and 50% MD/AG) and three
Encapsulation encapsulant concentration levels (10–20–30%) were used. MFJ was lyophilized at varying pressure (300 to
Spray drying 500 mTorr) with a varied freezing rate (0.3 °C/min to 0.7 °C/min). The MFJ spray-drying conditions were feed
Freeze drying flow (72–108–144 mL/h) and air temperature (80–100–120 °C). Second-order responses satisfactorily described
Storage the initial GA content as a function of independent variables to be determined. A higher initial GA content in
Phenolics the freeze-dried encapsulates was achieved with a wall blend ratio close to 100% AG and an encapsulant concen-
tration was 10 to 20% or with an MD concentration in the range of 80 to 100% when the chamber pressure was
greater than 400 mTorr, and the freezing rates were higher than 0.65 °C/min. For spray-drying, the best results
were found with the following drying conditions: Air Inlet Temperature, 85 to 105 °C; Feed Flow, 80 to
120 mL/h; Encapsulant Concentration, 10 to 20%; and Encapsulant Ratio, 50 to 80%. The MFJ models were also
suitable for the prediction of the initial polyphenol content in three encapsulated fruit pulps. The polyphenol
in the spray- and freeze-dried MFJ encapsulates showed first-order kinetics during a 200 day period of storage
at 25 °C with reaction rate coefficients fluctuating between 3 × 10−4 and 20 × 10−4 days−1 and between
7 × 10−4 and 50 × 10−4 days−1 respectively.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction pineapples, bananas, lemons, red and white wine, gallnuts, and witch
hazel are some of the natural products that are rich in gallic acid [4,5].
Fruits contain different antioxidant compounds, such as vitamin C, The effectiveness of polyphenols depends on their stability in food
vitamin E, carotenoids and polyphenols. Research on antioxidants in processing and storage, which is paradoxically poor due to their anti-
fruits has lately attracted great interest due to their potential protective oxidant power. Moreover, the phenolic bioavailability is negatively af-
effect in preventing the degenerative processes of cancer and cardiovas- fected in the conditions of the gastrointestinal tract. These are some of
cular and cerebrovascular diseases in humans [1]. the reasons why the concentrations of polyphenols that appear effective
Phenolics include thousands of compounds with different chemi- in vitro are often an order of magnitude higher than the levels measured
cal structures and comprise phenolic acids, flavonoids, stilbenes, and in vivo [2,6]. The use of encapsulated polyphenols instead of free com-
lignans. In addition to their anti-inflammatory, antibacterial, and anti- pounds can overcome these difficulties.
viral functions, many of them are stronger antioxidants than the vita- Encapsulation, which is a process for the entrapment of active com-
min antioxidants [2]. The dominant compound in the polyphenol pound into particles, can be achieved through various techniques, such
subgroup of hydroxy- and methoxy-benzoic acids is gallic acid (3,4,5- as spray-drying, spray-cooling/chilling, extrusion, fluidized bed coating,
trihydroxybenzoic acid), which is normally encountered in plant tis- coacervation, liposome entrapment, inclusion complexation, centrifugal
sues in ester form and is widely distributed in fruits and plants [3]. suspension separation, freeze- or vacuum-drying, cocrystallization,
Strawberries, gallnuts, sumac, oak bark, green tea, apple peels, grapes, nanoencapsulation, molecular inclusion and emulsion. Among these
techniques, spray-drying is the most often used in the food industry be-
⁎ Corresponding author. Tel.: +57 68879300x55831; fax: +57 68879400x55880.
cause it is economical and flexible and allows continuous operation [2].
E-mail addresses: mjramirezl@unal.edu.co (M.J. Ramírez), gigiraldogo@unal.edu.co Freeze-drying is a drying process for the long-term preservation of heat-
(G.I. Giraldo), corregoa@unal.edu.co (C.E. Orrego). sensitive food and other biological materials based on the phenomena

http://dx.doi.org/10.1016/j.powtec.2015.02.060
0032-5910/© 2015 Elsevier B.V. All rights reserved.
90 M.J. Ramírez et al. / Powder Technology 277 (2015) 89–96

of sublimation. A successful freeze-drying process preserves most of the (Colombia); gallic acid (analytical grade, 99%), Folin Ciocalteu reagent
initial raw material properties such as shape, dimensions, appearance, and sodium carbonate (anhydrous) were obtained from Sigma-
taste, color, flavor, texture and biological activity [7]. Different examples Aldrich (USA); gum arabic (acacia tree) was obtained from Ciacomeq
of fruit polyphenol encapsulation, including freeze-drying and spray- (Colombia); and maltodextrin (20DE) was purchased from Shandong
drying, can be found in recent reviews [2,6,8]. Bangye Co., Ltd. All of the used reagents were of analytical grade.
The materials used for the design of the protective shell of encapsu-
lates must be food-grade, biodegradable and able to form a wall or
barrier between the internal phase and its surroundings [9]. For encap- 2.2. Sample preparation
sulation purposes, the most common wall materials are maltodextrin,
gum arabic, and modified starch. These carbohydrate matrices increase The model fruit juice (MFJ) was prepared with 0.1% citrus pectin,
the glass transition temperature of the dried product, thereby trapping 10% sucrose and 0.5% gallic acid [15]. Before drying, each MFJ sample
the active compound in a vitreous phase that protects it against temper- was mixed with maltodextrin/gum arabic until the dispersion reached
ature, stickiness, collapse and enzymatic or chemical changes, such as the encapsulant concentration and encapsulant ratio defined by the
oxidation [6]. Maltodextrin (MD) is a hydrolyzed starch that is widely experimental design (Tables 1 and 2).
used in the encapsulation of bioactive compounds to protect them
from oxidative changes and temperature effects. It is usually a low-
cost option but has low emulsifying capacity. Gum arabic (AG) is a com- 2.3. Encapsulation by spray- and freeze-drying
plex heteroglycan with a highly ramified structure consisting of a main
chain formed of D-galactopyranose units joined by β-D-glycosidic bonds The spray-drying of the liquid dispersion of the encapsulants and
(1 → 3) [10]. AG presents many desirable characteristics of a good wall MFJ was performed with a mini Buchi model 191 spray dryer (Büchi
material for drying encapsulating techniques, such as an increase in the Laboratoriums Technik, Switzerland) under the following operating
glass transition temperature. It also imparts high solubility, low viscos- conditions: liquid feed volumetric flow rate, 72 to 144 mL/h; drying
ity and good emulsifying properties to feed dispersions. However, its air inlet temperature, 80 °C to 120 °C; nozzle air flow rate, 600 NL (liters
use as a wall material for encapsulation is restricted because of its cost at normal conditions)/h; and aspiration, 75% (28 m3/h).
and its varied and limited supply. Wall materials can be combined in Lyophilization was performed on a Genesis 25 freeze dryer (VirTis,
the search for a more efficient and stable carrier. A maltodextrin/pectin Gardiner, NY, USA) using the same sample heating profile. The following
(MD/PE) matrix was studied for the encapsulation of polyphenol-rich process conditions were varied: chamber pressure, 300 to 500 mTorr;
extracts via spray-drying. The MD/PE matrix was able to mask the and freezing rate, 0.3 °C/min to 0.7 °C/min. Freeze-drying was per-
unpleasant odor of the extracts and the product is rapidly soluble formed over a period of 16 ± 0.5 h.
in water [11]. After spray-drying or freeze-drying, each sample of encapsulated
Several studies on polyphenol encapsulation have been conducted. MFJ was ground into powder. Three grams of powder was separately
Most of these consider the encapsulation process by taking into consid- packed into metalized plastic bags (18 × 12 cm), and each bag was
eration the use of particular natural extracts (concentrated or not) using then vacuum-sealed.
different techniques and/or wall materials. This specificity makes it dif-
ficult to estimate whether the selection of a particular procedure may be
suitable for another raw material. In this study, a model juice or extract Table 1
with a typical composition and a fixed quantity of an accepted standard, Experimental conditions used for the spray-drying of model fruit juice (MFJ) for
the encapsulation of gallic acid and initial polyphenol powder contest obtained after
such as gallic acid, was used to develop appropriated predictive models spray-drying.
for the initial polyphenol content in encapsulates from different raw
materials. Gallic acid has been previously used as a model substance in Run Encapsulant Encapsulant Inlet Feed Polyphenol
concentration ratio temperature flow content
the study of spray-drying microencapsulation to evaluate the release (%) (°C) (mL/h) (mg of GA/100 mL)
behavior of GA from microparticles in water and the potential of nopal
1 30 100 100 108 383.3 ± 2.7
mucilage as wall material [12,13].
2 30 50 100 144 366.5 ± 2.5
Response surface methodology (RSM) is a very practical, economical 3 20 100 100 72 416.8 ± 2.2
and frequently used optimization technique for the modeling and anal- 4 20 50 100 108 495.5 ± 2.4
ysis of experimental data that tests several variables at a time and uses 5 20 50 120 144 397.4 ± 1.9
special experimental designs to reduce the number of required tests. 6 10 50 120 108 382.6 ± 1.8
7 20 50 100 108 497.9 ± 2.2
Response surface polynomials are local approximations of the real 8 10 50 100 144 493.7 ± 2.7
input-and-output relationships and can thus be used as an interesting 9 20 100 120 108 419.5 ± 3.8
alternative for conventional models, such as numerical simulations dur- 10 20 0 100 72 395.7 ± 2.3
ing optimization [14]. 11 30 50 120 108 382.7 ± 1.5
12 20 0 120 108 337.8 ± 1.5
In this study, a model juice was used to evaluate the effect of differ-
13 20 50 80 72 492.0 ± 1.1
ent amounts of two encapsulants (MD and AG) and operational vari- 14 10 50 100 72 432.6 ± 0.9
ables for two encapsulating techniques (freeze- and spray-drying) on 15 30 50 80 108 404.1 ± 1.1
the gallic acid content and stability of a dried powder sample using 16 10 50 80 108 449.9 ± 2.3
response surface methodology (RSM). A secondary aim of this paper 17 30 50 100 72 421.2 ± 0.7
18 20 0 80 108 401.1 ± 0.6
was to investigate the effect of operational variables on the stability of 19 20 50 80 144 383.4 ± 1.3
the gallic acid content in the encapsulated powders over a long-term 20 20 100 100 144 440.9 ± 1.7
storage period (200 days). 21 10 100 100 108 481.5 ± 0.6
22 10 0 100 108 372.8 ± 2.0
23 30 0 100 108 437.7 ± 1.6
2. Materials and methods
24 20 50 100 108 496.3 ± 2.1
25 20 50 120 72 363.3 ± 1.2
2.1. Materials and reagents 26 20 50 100 108 493.9 ± 0.7
27 20 100 80 108 388.3 ± 2.2
Commercial sucrose (98% purity) was used in this study; citrus pec- 28 20 50 100 108 494.4 ± 2.0
29 20 0 100 144 428.4 ± 2.4
tin (degree of esterification, 63–66%) was obtained from Protokimica
M.J. Ramírez et al. / Powder Technology 277 (2015) 89–96 91

Table 2 the feed flow and the air inlet temperature, and in freeze-drying, the
Experimental conditions used for the freeze-drying of model fruit juice (MFJ) for most important variables are the chamber pressure and the sample
the encapsulation of gallic acid and initial polyphenol powder contents obtained after
freeze-drying.
freezing rate. To study the combined effect of these factors, experiments
were performed using different combinations based on a three-level
Run Encapsulant Encapsulant Freezing Chamber Polyphenol content factorial design. In addition to considering the operational limitations
concentration ratio rate pressure (mg of GA/100 mL)
of the available equipment, the selection of the operational ranges of
(%) (°C/min) (mTorr)
the variables was guided by previous studies and pre-experimentation
1 20 0 0.5 300 470.8 ± 1.3
results to ensure that stable powders with a water activity of 0.40 ±
2 30 50 0.5 300 396.6 ± 3.0
3 20 50 0.5 400 379.3 ± 1.0 0.08 and a moisture content of less than 5.0% (wet basis) are obtained.
4 20 0 0.3 400 498.6 ± 1.5 The tests for the spray-drying of the MFJ-encapsulant dispersion consid-
5 10 0 0.5 400 439.1 ± 1.9 ered four independent variables: A, encapsulant concentration related
6 20 50 0.5 400 372.0 ± 1.2 to the mass of the MFJ-encapsulant dispersion sample (10–20–30%);
7 20 50 0.3 300 449.7 ± 2.0
8 20 100 0.7 400 468.0 ± 0.9
B, encapsulant ratio or AG content (%) in the encapsulant mixture
9 10 100 0.5 400 494.0 ± 2.2 (B = 0, 0% AG or 100% MD; B = 100, 100% AG; and B = 50, 50% MD
10 10 50 0.7 400 434.3 ± 2.0 and 50% AG) used in MFJ-encapsulant feed dispersion; C, air inlet tem-
11 30 50 0.5 500 400.5 ± 1.8 perature (80–100–120 °C); and D, feed flow (72–108–144 mL/h). For
12 20 50 0.3 500 438.4 ± 0.4
freeze-drying, a similar three-level factorial design was used with the
13 20 50 0.7 300 483.7 ± 2.2
14 30 100 0.5 400 404.9 ± 1.5 following four independent factors: A, encapsulant concentration related
15 30 50 0.7 400 441.9 ± 1.6 to the mass of the MFJ-encapsulant dispersion sample (10–20–30%); B,
16 20 50 0.5 400 381.8 ± 0.9 encapsulant ratio (0–50–100%) in the MFJ-encapsulant feed dispersion;
17 10 50 0.5 500 494.2 ± 2.9 C, freezing rate (0.3–0.5–0.7 °C/min); and D, chamber pressure (300–
18 30 50 0.3 400 397.1 ± 2.5
400–500 mTorr). All of the analyses of the initial polyphenol contents
19 20 0 0.5 500 489.1 ± 2.4
20 30 0 0.5 400 495.6 ± 2.7 of the dehydrated powders were performed in triplicate.
21 20 100 0.5 300 458.8 ± 2.7
22 20 0 0.7 400 494.2 ± 2.0 2.8. Statistical analysis
23 20 50 0.7 500 483.1 ± 0.8
24 20 100 0.3 400 455.9 ± 1.5
25 10 50 0.5 300 491.5 ± 2.2
The results of the experimental design were analyzed using the
26 10 50 0.3 400 491.7 ± 2.4 Design Expert® software version 8.0 (StatEase, Inc., Minneapolis, MN,
27 20 100 0.5 500 480.1 ± 0.6 USA) with a second-order polynomial equation to determine the coeffi-
28 20 50 0.5 400 377.2 ± 0.9 cients of the response model as well as their standard errors and signif-
29 20 50 0.5 400 377.4 ± 0.8
icance. For the four input variables under consideration, the response
model was as shown in Eq. (1):
2.4. Encapsulate stability in storage conditions
X
k X
k
2
XX
The packed encapsulated MFJ samples were stored at 25 °C under a Y ¼ β0 þ β jX j þ β j jX j þ βi j X i X j ð1Þ
62 ± 1% RH atmosphere. j¼1 j¼1 ib j

Their total phenolic content was periodically measured over a period


of 200 days. For each run (see Tables 1 and 2), a plastic bag was random- where Y is the predicted response (initial polyphenol content), ß0, ßi, ßii
ly selected, and the powder water activity was measured. Then, before and ßij are the regression coefficients for the intercept and the linear,
any additional analysis, the powder was rehydrated until the MFJ- quadratic and interaction coefficients, respectively, Xi and Xj are inde-
encapsulant water dispersion reached the same solid content measured pendent variables, and k = 4, i.e., the number of independent variables.
prior to drying. The quality of the model fits was evaluated by the coefficients of
determination (R2 and adjusted R2), analysis of variance (ANOVA) and
2.5. Moisture content and water activity absolute average deviation (AAD) analysis. The model was refined
after insignificant coefficients were examined and manually eliminated.
The initial and storage evolution of the water activity and moisture
content of the encapsulated MFJ were measured using a water activity 3. Results and discussion
meter (Decagon, model 99163, Pawkit, USA) and an infrared moisture
analyzer (Model LJ16 Mettler-Toledo, Switzerland) at 80 °C. 3.1. Polyphenol content

2.6. Total polyphenol content According to the experimental design, a total of 29 experiments
were run for each encapsulation technique to assess the initial polyphe-
The sample extractions were performed for 24 h (25 °C, constant nol content in dried MFJ. The actual independent variables and the
stirring at 100 rpm) with a solution of 80% aqueous methanol at a resulting sample polyphenol content data for the spray-drying and
1: 4 (w/v) ratio. The samples were then centrifuged (2000 g, 30 min, freeze-drying experiences are shown in Tables 1 and 2, respectively.
25 °C). The total polyphenol content of the supernatant was determined Table 3 shows the results of the quadratic surface-model fitting
through the Folin–Ciocalteu method with some modifications [16]. The for the polyphenol content response. The statistical significance of the
absorbance was read at 765 nm on a Jenway UV/Visible spectrophotom- ratio of the mean square variation due to regression to the mean square
eter (Model 6405, England). Total polyphenol content was expressed as residual error was tested through an analysis of variance (ANOVA). The
mg of gallic acid per 100 mL of sample. greater the F value is from unity, the more certain it is that most of the
variation in the response can be explained by the regression equation.
2.7. Experimental design In contrast, a small value for the computed error probability, namely
the p value, indicates that the regression model is more significant. If
The encapsulant concentrations and encapsulant ratio are significant p N F value is lower than 0.05, the model is statistically significant.
parameters that affect the polyphenol content in spray- and freeze- The regression coefficients and p values for the initial polyphenol re-
drying. The most important operational variables in spray-drying are sponse due to spray-drying and freeze-drying are tabulated in Table 3.
92 M.J. Ramírez et al. / Powder Technology 277 (2015) 89–96

Table 3 model, an absolute average deviation (AAD) analysis was performed


Analysis of variance (ANOVA) of the regression coefficients and their p-values in quadratic on the data. The AAD is calculated by the following equation:
models for predicting the optimized responses for spray-drying and freeze-drying.
2   3
 
Spray-drying Freeze-drying Xp Y i;exp −Y i;calc =Y i;exp
AAD ¼ 100 4 5 ð4Þ
Factor Coefficient p-Value Factor Coefficient p-Value i¼1 p
+02 +03
Intercept −7.960 × 10 Intercept 1.612 × 10
A 1.813 × 10+01 0.0042 A −1.484 × 10+01 0.0004
B 1.450 × 10+00 0.0226 B −1.305 × 10+00 0.0803 where Yi, exp and Yi, cal are the experimental and calculated responses, re-
C 2.077 × 10+01 0.0025 C −1.368 × 10+03 0.2831 spectively, and p is the number of experimental runs. The evaluation of
D 1.760 × 10+00 0.9328 D −3.471 × 10+00 0.6104 the R2 and AAD values together should provide a better confirmation of
AB −8.156 × 10−02 0.0005 AB −7.231 × 10−02 0.0020
the accuracy of the model. The values of R2 must be close to 1.0, and the
AC 5.737 × 10−02 0.2377 AC 1.277 × 10+01 0.0181
AD −8.040 × 10−02 0.0073 AD 2.869 × 10−04 0.9765 AAD between the predicted and the observed data must be as small as
BC 2.541 × 10−02 0.0096 BC 4.130 × 10−01 0.6719 possible [17].
BD −2.033 × 10−03 0.6751 BD 1.471 × 10−04 0.9397 The AAD values of the spray-drying and freeze-drying models were
CD 4.954 × 10−02 0.0017 CD 1.338 × 10−01 0.7834 found to be 2.60% and 2.43%, respectively, which means that the models
A2 −3.229 × 10−01 0.0007 A2 2.350 × 10−01 0.0073
B2 −1.881 × 10−02 b0.0001 B2 2.278 × 10−02 b0.0001
for the response (initial polyphenol content of the encapsulates) are
C2 −1.474 × 10−01 b0.0001 C2 1.069 × 10+03 b0.0001 acceptable.
D2 −2.323 × 10−02 0.0011 D2 4.275 × 10−03 b0.0001

A, encapsulant concentration; B encapsulant ratio. 3.2. Reproducibility of the models


Spray-drying: C, inlet temperature; D, feed flow.
Freeze-drying: C, freezing rate; D, chamber pressure. The suitable values of R2 and AAD values obtained in this study indi-
cate that the model equations explain the real behavior of the systems
Most of the variables, with the exception of the terms required to retain and can be used for interpolation in the experimental domain. Never-
hierarchy of the models, have p values, less than 0.01. theless, the reproducibility of each of the models was assessed by
The second-order response function representing the relationship selecting six independent variable conditions different from those
between the initial polyphenol content (mg GA/100 mL) and the inde- used in the original experimental design for each encapsulation
pendent variables in the spray-drying process, namely A (Encapsulant
Concentration in MFJ), B (Encapsulant Ratio), C (Inlet Temperature), Table 4
and D (Feed Flow), is the following: Reproducibility tests of the proposed mathematical models (Eqs. (2) and (3)) for polyphe-
nol encapsulation by spray- and freeze-drying. The polyphenol content is expressed as mg
of GA/100 mL of reconstituted MFJ or pulp.
Polyphenol content ¼ −796:020 þ 18:125A þ 1:450B þ 20:769C
2
þ1:760D–0:082AB–0:080AD þ 0:025BC þ 0:050CD–0:323A ð2Þ Test A B C D Polyphenol Polyphenol content Difference
2 2 2 (%) (ratio) (°C) (mL/h) content (experimental (%)
−0:019B –0:147C –0:023D : (predicted) values)

Spray-drying
All first-order coefficients of the model for the polyphenol response 1 30 15 80 72 439.81 458.31 ± 1.51 4.04
have positive effects, whereas the quadratic coefficients have a negative 2 25 20 90 90 472.70 465.70 ± 1.09 1.50
effect. Most interaction coefficients have relatively small effects on the 3 20 40 100 108 490.55 487.26 ± 2.58 0.67
initial polyphenol content of the spray-dried encapsulates. In general, 4 10 50 110 126 466.51 490.53 ± 3.09 4.90
5 25 60 120 144 397.22 391.07 ± 2.36 1.57
the air inlet temperature (C) has the most significant effect on the re-
6 15 80 90 126 478.60 472.36 ± 2.07 1.32
sponse, followed by the encapsulant concentration (A). P1 20 50 100 108 104.99 98.13 ± 1.01 6.99
The relationship between the polyphenol content (mg GA/100 mL) P2 10 100 100 108 103.42 97.35 ± 0.88 6.24
and the independent variables in the freeze-drying process, namely A P3 10 50 100 72 89.56 91.35 ± 1.26 1.96
(Encapsulant Concentration in MFJ), B (Encapsulant Ratio), C (Freezing B1 20 50 80 144 287.85 280.30 ± 1.40 2.69
B2 10 50 100 72 312.58 338.20 ± 0.90 7.57
Rate), and D (Chamber Pressure), can be represented by the following B3 20 50 120 144 312.47 302.60 ± 0.80 3.26
equation: M1 10 50 100 72 240.15 261.80 ± 1.80 8.27
M2 10 50 100 108 273.47 254.80 ± 1.00 7.33
Polyphenol content ¼ 1612:222–14:845A–1:305B–1368:220C–3:471D M3 20 50 120 144 240.06 243.90 ± 1.00 1.58
2 2 2 2
–0:072AB þ 12:773AC þ 0:235A þ 0:023B þ 1069:365C þ 0:004D :
Freeze-drying
ð3Þ 1 30 25 0.3 300 468.73 457.01 ± 4.05 2.57
2 25 20 0.4 350 420.75 412.10 ± 3.18 2.10
In contrast with the spray-drying model, all first-order coefficients of 3 20 40 0.5 400 381.90 374.72 ± 1.05 1.92
4 10 50 0.6 450 440.29 446.43 ± 1.31 1.38
the polynomial for the polyphenol response have negative effects,
5 25 60 0.7 470 454.76 465.70 ± 2.97 2.35
whereas the quadratic coefficients have a positive effect. The interaction 6 15 80 0.3 320 495.21 448.86 ± 1.47 10.33
coefficient between the encapsulant concentration and the freezing rate P1 20 0 0.3 400 107.90 110.06 ± 1.01 1.96
has a positive effect on the initial polyphenol content of freeze-dried P2 30 0 0.5 400 106.41 109.71 ± 0.88 3.00
P3 10 50 0.5 500 104.86 104.33 ± 1.75 0.51
encapsulates.
B1 10 50 0.5 500 415.35 444.50 ± 0.90 6.56
The coefficient of determination (R2) and the adjusted R2 of the B2 20 100 0.3 400 401.83 430.20 ± 3.80 6.59
spray-drying model were 0.9179 and 0.8414, respectively, and for the B3 20 50 0.5 400 332.25 357.40 ± 1.90 7.04
freeze-drying model, the values of these parameters were 0.9085 and M1 10 50 0.5 500 278.63 283.30 ± 0.10 1.65
0.8170, respectively. The analysis of variance (ANOVA) showed no M2 20 100 0.3 400 269.56 239.60 ± 0.60 12.50
M3 20 50 0.5 400 222.89 230.50 ± 1.10 3.30
lack of model fit. Although the overall predictive capability of the
model is commonly explained by these coefficients and the test of the See Section 2.7 for a description of the abbreviations of A, B, C and D. P = passion fruit;
B = blackberry; M = mango.
lack of fit, a large value of R2 does not necessarily imply that the regres-
Average polyphenol contents (mg of GA/100 mL) in the fruit pulps obtained through the
sion model is good because it is possible for models that have large spray-drying tests: 106.50 (P), 370.12 (B), 284.35 (M).
values of R2 to yield poor predictions of new observations or estimates Average polyphenol contents (mg of GA/100 mL) of fruit pulps obtained though the
of the mean response. To further verify the accuracy of the selected freeze-drying tests: 111.09 (P), 440.02 (B), 295.18 (M).
M.J. Ramírez et al. / Powder Technology 277 (2015) 89–96 93

technique (Tables 1 and 2). The results of these confirmatory tests for drying response. Using these variables as axes y and x, respectively,
spray-drying and freeze-drying, are presented in Table 4. the contour plots of the estimated responses (Fig. 2) display ellipses,
Table 4 also included three lines that describe the data obtained from and their central zones are the regions in which the maximal initial
tests using three real fruit pulps (passion fruit, Passiflora edulis L.; black- polyphenol contents were reached.
berry, Rubus glaucus Benth; and mango, Mangifera indica). The results The use of a relatively high air temperature entails considerable risk
obtained from the reproducibility tests were found to be comparable of thermal degradation in the spray-drying encapsulation of bioactives.
with the model predictions. The AAD values between the predicted Nevertheless, polyphenols are generally considered thermostable [18].
and observed data from the reproducibility tests for spray-drying and Indeed, gallic acid has an endothermic melting phase transformation
freeze-drying were 2.43% and 4.25%, respectively. Thus, the second- between 258 and 260 °C [19]. Thus, in the spray-drying assays, heating
order regression functions (Eqs. (2) and (3)) are adequate for prediction the air temperature should not cause a marked decrease in the gallic
within the range of the experimental variables for the MFJ. In addition, acid/polyphenol content of the encapsulates. However, when a certain
these models may also be suitable for real fruits because they provided high air inlet temperature is reached, the resulting excessive evapora-
acceptable predictions of the polyphenol content after spray-drying and tion could result in fissures and deformations in the wall materials,
freeze-drying encapsulation with maltodextrin and gum arabic for the causing premature release of their contents and degradation of the
three different fruit pulps tested. encapsulated ingredient. According to the spray-drying contour plots
(Fig. 1(c) and (d)), the safest range of temperatures found in this
3.3. Comparison of the response contour plots of the initial polyphenol study was 85 to 105 °C for all wall materials tested. Taking into account
content the abovementioned thermal stability of gallic acid, the marginal (but
cumulative with an increase in the air temperature) losses of polyphe-
A better understanding of the effects of variables on the initial poly- nol in the encapsulates produced at temperatures greater than 105 °C
phenol content response can be determined from the two-dimensional were likely due to the release and oxygen decomposition of the phenolic
display of the surface plot or contour plots in which lines of constant re- molecules across the cracked walls of the microspheres obtained at
sponse are drawn in the plane of the independent variables. Figs. 1 and 2 these temperatures.
show the contour plots of the spray-drying and freeze-drying encapsu- Igual et al. studied the spray-drying encapsulation of lulo pulp
lates for both sets of independent process variables (A, B, C and D, as de- (Solanum quitoense Lam.) and observed that the initial polyphenol con-
scribed in Section 2.7). tent in the MFJ encapsulates was generally positively affected by an in-
According to Eq. (2), the air inlet temperature (C) and encapsulant crease in the gum arabic/maltodextrin feed solute concentration and a
concentration (A) have the most significant effects on the spray- decrease in the air inlet temperature [20]. In the present study, this

Fig. 1. Model contour plots for the initial polyphenol content of spray-dried encapsulates as a function of the air inlet temperature and encapsulant concentration. (a) Encapsulant ratio = 0%,
flow rate = 108 mL/h. (b) Encapsulant ratio = 50%, flow rate 72 = mL/h. (c) Encapsulant ratio = 80%, flow rate = 120 mL/h. (d) Encapsulant ratio = 50%, flow rate = 108 mL/h.
94 M.J. Ramírez et al. / Powder Technology 277 (2015) 89–96

Fig. 2. Model contour plots for the initial polyphenol content of freeze-dried encapsulates as a function of the freezing rate and encapsulant concentration. (a) Encapsulant ratio = 0%,
pressure = 400 mTorr. (b) Encapsulant ratio = 20%, pressure = 500 mTorr. (c) Encapsulant ratio = 50%, pressure = 500 mTorr. (d) Encapsulant ratio = 100%, pressure = 500 mTorr.

response was only detected when using maltodextrin-rich wall mate- content of the corresponding encapsulates achieved the highest values
rials (low B value, Fig. 1(a)). However, when the encapsulant ratio (480–500 mg GA/100 mL), independently of the other input parameters
was increased (high B values, Fig. 1(c) and (d)), the optimal range for (Fig. 2(a) to (d)). In-freeze drying, the product structure is mainly de-
polyphenol preservation in the spray-drying assays (480–500 mg GA/ veloped during the previous freezing step. In general, fast freezing
100 mL) was determined. Successful encapsulation using wall materials rates generate small ice crystals, and conversely, a slow cooling rate
with a high gum arabic to maltodextrin ratio has been reported else- generates large crystals. At lower freezing rates, the larger ice crystals
where [21,22]. In spray-drying encapsulation, the ideal types of wall result in larger pore diameters in the dried sample structure as ice sub-
materials must have a low water effective diffusivity and a high activa- limation proceeds. On the contrary, fast freezing rates lead to the devel-
tion energy (the energy required for evaporating a mass of water from opment of low-porosity structures. However, the samples frozen at
the material to be dried). Taking into account that AG/MD blends con- higher freezing rates (0.65 to 0.70 °C/min) also showed high initial poly-
taining a large proportion of gum arabic have slightly higher activation phenol contents in the dried encapsulates. Heinzelmann and Franke
energies than wall materials composed of an individual biopolymer and studied the microencapsulation of fish oil and found that the slowest
consequently require more energy to build (and enter) the wall, high and the fastest freezing rates led to the best results in terms of oxidation
AG/MD blends may provide superior protection against the oxidative stability [23]. In contrast, a better retention of ascorbic acid in the
processes of the encapsulated molecules [21]. freeze-dried soursop fruit pulp encapsulated with MD was associated
According to the abovementioned analysis, the best gallic acid with lower sample freezing rates [7].
preservation (480–500 mg GA/100 mL MFJ) in this study was obtained The results also revealed that a high initial polyphenol content was
within the following optimal ranges for the independent variables con- achieved when the pressure reached values greater than 400 mTorr
sidered in the spray-drying process: A (Encapsulant Concentration in in the range of chamber pressures studied (Fig. 2(b) and (d)), and at
MFJ), 10–20%; B (Encapsulant Ratio), 50–80%; C (Inlet Temperature), maximal pressure (500 mTorr), the modeled effect of the freezing rate
85–105 °C; and D (Feed Flow), 80–120 mL/h. on this response vanished (Fig. 2(d)). Freeze-drying at high pressure
Based on the freeze-drying assays, Fig. 2 shows the interaction be- implies an increase in the sublimation temperature and consequently
tween the freezing rate (C) and the encapsulant concentration (A). As a reduction in the complex viscosity of the material, leading to the accel-
in the spray-drying contour plots, the contour plots shown in Fig. 2 eration of shrinkage, an increase in the apparent density and a decrease
also display ellipses, but in this case, their centers refer to a minimal in porosity [24].
contents of polyphenol in the encapsulates. When the freezing rate Similar to the results for the spray-drying tests, higher concentra-
was fixed to its lower range (0.3–0.35 °C/min), the initial polyphenol tions of polyphenol in the encapsulates (480–500 mg GA/100 mL of
M.J. Ramírez et al. / Powder Technology 277 (2015) 89–96 95

Table 5
Characteristics of encapsulates at the start and at end of the storage period (200 days, 22 °C).

Run a Polyphenol content (mg of GA/100 mL) PRb (%) Moisture content wet basis (%) Water activity

Initial Final Initial Final Initial Final

Spray-drying
4 495.5 ± 2.4 380.9 ± 1.5 76.9 3.9 ± 0.1 6.7 ± 0.1 0.38 ± 0.02 0.41 ± 0.01
7 497.9 ± 2.2 394.0 ± 1.1 79.1 3.8 ± 0.1 6.6 ± 0.1 0.41 ± 0.01 0.49 ± 0.02
9 419.5 ± 3.8 379.9 ± 2.6 90.6 4.5 ± 0.2 6.4 ± 0.2 0.43 ± 0.01 0.50 ± 0.01
14 432.6 ± 0.9 412.9 ± 3.1 95.4 4.1 ± 0.2 6.5 ± 0.2 0.42 ± 0.01 0.49 ± 0.01
19 383.4 ± 1.3 326.3 ± 2.4 85.1 5.1 ± 0.2 6.3 ± 0.1 0.44 ± 0.02 0.46 ± 0.01
21 481.5 ± 0.6 333.4 ± 2.1 69.2 4.3 ± 0.2 6.5 ± 0.2 0.40 ± 0.01 0.46 ± 0.01
24 496.3 ± 2.1 461.9 ± 0.9 93.1 3.8 ± 0.1 6.1 ± 0.2 0.39 ± 0.01 0.41 ± 0.01
26 493.9 ± 0.7 376.6 ± 2.3 76.3 4.0 ± 0.1 6.8 ± 0.3 0.42 ± 0.01 0.48 ± 0.02

Freeze-drying
4 498.6 ± 1.5 332.4 ± 2.8 66.7 2.9 ± 0.1 5.5 ± 0.3 0.36 ± 0.01 0.41 ± 0.01
9 494.0 ± 2.2 357.5 ± 1.1 72.4 2.7 ± 0.1 6.1 ± 0.2 0.34 ± 0.01 0.40 ± 0.01
12 438.4 ± 0.4 322.3 ± 1.3 73.5 2.1 ± 0.2 6.6 ± 0.2 0.29 ± 0.01 0.37 ± 0.02
17 494.2 ± 2.9 332.4 ± 2.6 67.3 3.1 ± 0.1 5.9 ± 0.2 0.37 ± 0.01 0.46 ± 0.01
20 495.6 ± 2.7 431.4 ± 1.4 87.0 2.8 ± 0.2 5.8 ± 0.2 0.35 ± 0.01 0.37 ± 0.01
24 455.9 ± 1.5 247.4 ± 0.7 54.3 2.6 ± 0.2 6.1 ± 0.1 0.33 ± 0.01 0.52 ± 0.01
26 491.7 ± 2.4 381.3 ± 1.2 77.5 2.8 ± 0.2 6.2 ± 0.1 0.35 ± 0.02 0.39 ± 0.01
29 377.4 ± 0.8 166.5 ± 1.6 44.1 2.4 ± 0.1 7.6 ± 0.2 0.32 ± 0.01 0.55 ± 0.02
a
See Tables 1 and 2 for experimental conditions of runs.
b
PR = Percentage of retention according to the initial and final polyphenol average values.

reconstituted MFJ) were found with wall blends close to 100% AG MFJ) as a function of time during the period of storage (data not shown),
(Fig. 2(d)). The freezing rate did not affect the response for this type showing good agreement with first-order kinetics (R2 between 0.90
of wall material at the optimal range of encapsulant concentration of and 0.99). The initial and final values of the polyphenol content, water
10–20%. However, comparable successful polyphenol preservation was activity and moisture content of the encapsulate samples (at the begin-
observed for wall materials with a high MD concentration (80 to 100% ning and end of this experiment, respectively) are shown in Table 5.
or 0 b B b 20), particularly when the chamber pressure was greater Moisture acts as a plasticizer in wall materials. An increased moisture
than 400 mTorr (Fig. 2(a) and (b)). In this case, to achieve the same content in the sample will reduce the glass transition temperature, which
high level of polyphenol in encapsulates (490–500 mg GA/100 mL of results in an increase in the rate of physicochemical changes in dried
reconstituted MFJ), it was necessary to use freezing rates higher than products, such as oxidation [26]. During the 200 days of storage used in
0.65 °C/min, regardless of the concentration of encapsulate used, or less the stability tests, both the moisture content and the water activity (aw)
than 0.4 °C/min with an encapsulant concentration of A b 20%. A few of the samples increased slightly (see Table 5). The absorption of water
studies have investigated antioxidant encapsulation using freeze-drying and the consequent increase in water activity increase the barrier plastic-
with MD, AG or their mixtures as the wall materials. In one of these ity of the wall materials and facilitate the polyphenol content depletion.
studies, the polyphenol content of red wine powder encapsulated with In this study, the reaction rate coefficients for spray-dried and freeze-
20% (w/w) DE10 MD, was preserved up to 97.8% compared with the dried encapsulates varied between 3 × 10−4 and 20 × 10−4 days−1
polyphenol content in the wine solution before freeze-drying [25]. (25 °C) and between 7 × 10−4 and 50 × 10−4 days−1 (25 °C), respective-
According to the plots shown in Fig. 2 and Eq. (3), the optimal ranges ly. In Table 6, the results of the shelf-life analysis performed in this study
of the independent variables for the freeze-drying process considered in are compared with the results of other studies that discovered first-order
this study that resulted in the best preservation (480–500 mg GA/ degradation rates under different storage conditions. Higher first-order
100 mL MFJ) of a constant input content of gallic acid (500 mg GA/ degradation rate coefficients were found in similar polyphenol encap-
100 mL MFJ) were the following: A (Encapsulant Concentration in sulate stability studies: 130 × 10−4 days−1 (40 °C) for freeze-dried
MFJ), 10–12%; B (Encapsulant Ratio), 80–100%; C (Freezing Rate), Hibiscus sabdariffa [27], 780 × 10−4 days−1 (44 °C) for cactus pear
0.30–0.35 °C/min; and D (Chamber Pressure), 475–500 mTorr. spray-dried with maltodextrin [28], and 60 × 10−4 days−1 (30 °C) for
freeze-dried roselle extract [29]. It is important to note that there are
3.4. Storage stability of encapsulated model fruit juice other factors that can influence phenolic antioxidant degradation, such
as light, oxygen and water availability, the chemical structure, the initial
The total phenolic content of some selected packed samples of MFJ concentration of antioxidant and the presence of other food components.
encapsulates was periodically measured over a period of 200 days. Lin- The data obtained from the self-life analysis demonstrate that spray-
ear relationships were observed in the plots of Ln(gallic acid/100 mL of drying is a superior technique for the encapsulation of the gallic acid in

Table 6
First-order storage degradation rates of the polyphenol contents of different encapsulates.

Raw material Polyphenol Product k ∗ 102 Days Storage temperature Reference


(day−1) (°C)

Cactus pear (Opuntia ficus-indica) Betacyanin Micro-encapsulated by spray drying with maltodextrin. 7.8 44 60 [28]
Roselle Anthocyanin Freeze–dried roselle extract. 0.3–0.6 105 30 [29]
Hibiscus sabdariffa L. Anthocyanin Freeze–dried extract. 2.3 75 40 [27]
Hibiscus sabdariffa L. Anthocyanin Encapsulated by freeze drying with pullulan. 1.3 75 40 [27]
Model fruit juice Gallic acid Micro-encapsulated by spray drying with maltodextrin 0.03–0.2 200 25 This work
and gum arabic. 0.09–0.6 200 40 Estimated a
Model fruit juice Gallic acid Encapsulated by freeze drying with maltodextrin and 0.07–0.5 200 25 This work
gum arabic 0.2–1.3 200 40 Estimated a
a
Activation energy: 13 kcal/mol, average value reported for thermal stability studies of spray- and freeze-dried encapsulated antioxidants [27,30].
96 M.J. Ramírez et al. / Powder Technology 277 (2015) 89–96

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This research was supported by Colciencias (code1119-502-27411
CT 673-2011) and DIMA-Universidad Nacional de Colombia sede Mani- Mónica Julieth Ramírez Londoño received her B.S. and
zales (Hermes project codes 12691 and 15299). M.Sc. degrees in Chemical Engineering at the Universidad
Nacional de Colombia. She currently works as a Purchasing
Coordinator of Packing Materials and New Developments at
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