LWT - Food Science and Technology 43 (2010) 1419e1425

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LWT - Food Science and Technology

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Influence of CaCl2 on the water vapor permeability and the surface morphology
of mesquite gum based edible films
E. Bosquez-Molina a, *, S.A. Tomás b, M.E. Rodríguez-Huezo a
a
Departamento de Biotecnología, Universidad Autónoma MetropolitanaeIztapalapa, Av. San Rafael Atlixco 186 Col., Vicentina Iztapalapa. CP. 09340. México, D.F, México
b
Departamento de Física, Centro de Investigación y de Estudios Avanzados-IPN, AP 14-740, México 07300 D.F., México

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

Article history: Oil-in-water (O/W) emulsions with a dispersed phase mass fraction (4m) of 0.175 were prepared by
Received 31 March 2009 dispersing a blend of candelilla wax/mineral oil (2:1 ratio) in 10 g of mesquite gum per 100 g of water
Received in revised form containing either CaCl2 (0.0, 0.1, 0.2, 0.3, 0.4 or 0.5 g) alone or combined with 1.5 g of glycerol. The mean
12 April 2010
volumetric droplet size (d3,0), the rate of droplet coalescence (C) and the viscosity-shear rate behavior of
Accepted 13 April 2010
the emulsions were affected by the addition of CaCl2 alone or combined with glycerol. The Carreaue
Yasuda model fitted best the viscosity-shear rate data of all the emulsions. The surface morphology of the
Keywords:
edible films, analyzed by Atomic Force Microscopy (AFM), exhibited a strong dependence on the CaCl2
Edible films
Mesquite gum
concentration. Maximum roughness occurred with a CaCl2 concentration of 0.3 g per 100 g. Films with
Atomic force microscopy glycerol showed significantly higher roughness than those with only CaCl2. Water vapor permeability
Water vapor permeability (WVP) was significantly lowered as the concentration of CaCl2 increased from 0.1 to 0.3 g per 100 g in the
coatings, but increased again at CaCl2 concentrations of 0.4e0.5 g per 100 g. Coatings containing glycerol
displayed significant higher WVP.
Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction Bósquez-Molina & Vernon-Carter, 2005). It is well known that the

The development of edible coatings and films has increasingly
attracted the attention of researchers, mainly due to the large
variety of applications given by these materials. Particularly, the
capability of edible films to regulate moisture, lipid migration, and
gas transport, can be used to improve food quality and extend the
shelf life of foodstuff. In addition, edible films play an important
role in the covering of thermolabile compounds like vitamins,
aroma, and flavors, providing an efficient method to preserve their
characteristics during food processing (Aguilar-Méndez, Martín-
Martínez, Tomás, Cruz-Orea, & Jaime-Fonseca, 2008; Cuppett,
1994; Tomás et al., 2004).
Edible film and coating formulations consist of different
components which directly affect the nature and properties of the
synthesized film. Previous studies have shown that composite
coatings formulated with a blend of candelilla wax and mineral oil
(at 2:1 ratio) as the lipid phase, and mesquite gum as the structural
material, have potential as edible coatings, but improvement of
their mechanical and water barrier properties is still desirable
(Bósquez-Molina, Guerrero-Legarreta, & Vernon-Carter, 2003;
* Corresponding author.
E-mail address: elbm@xanum.uam.mx (E. Bosquez-Molina).
ability of hydrophobic substances to retard moisture transfer
depends on the homogeneity of their final distribution in the
matrix and the functionality of the latter is also affected by its
interactions with other chemical components.
Mesquite gum (MG) is a natural polysaccharide exuded by the
bark of Prosopis spp. trees. Previous studies have demonstrated that
the functionality of mesquite gum is comparable and even superior,
in certain conditions, to that of gum Arabic (Acacia senegal) (GA)
(Goycoolea, Calderón de la Barca, Balderrama, & Valenzuela, 1997;
Vernon-Carter, Beristain, & Pedroza-Islas, 2000), which is consid-
ered a benchmark emulsifying, encapsulating, and film forming
agent (Garti & Leser, 2001). Chemically, both gums are highly
branched complex heteropolyelectrolytes formed principally by L-
arabinose and D-galactose, and minor proportions of 4-O-methyl-D-
glucuronate, and L-rhamnose, differing only in the ratio between
these residues, being of 2:4:1:1 for MG, and 4:2:1:1 for GA,
respectively. MG and GA have been reported as containing a small
amount of protein, being from 2.0 to 4.8% for MG, and from 1.0 to
2.0% for GA, which are complex mixtures of distinct fractions with
different chemical structures (Goycoolea, Calderón de la Barca,
Balderrama, & Valenzuela, 1998; Orozco-Villafuerte, Cruz-Sosa,
Ponce-Alquicira, & Vernon-Carter, 2003; Ray, Bird, Iacobucci, &
Clark, 1995; Román-Guerrero, Orozco-Villafuerte, Pérez-Orozco,
Cruz-Sosa, Jiménez-Alvarado, & Vernon-Carter, 2009). This protein

0023-6438/$ e see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.lwt.2010.04.023
1420 E. Bosquez-Molina et al. / LWT - Food Science and Technology 43 (2010) 1419e1425

fraction is largely responsible for the excellent emulsifying and
film forming capacity of MG and GA since the amino acid residues
anchor at the interface and the hydrophilic carbohydrate blocks
extend into the aqueous solution, preventing droplet flocculation
and coalescence due to steric effects (Dickinson, 2003; López-Franco,
Goycoolea, Valdez, & Calderón de la Barca, 2006; Orozco-Villafuerte
et al., 2003; Vernon-Carter et al., 2000). MG has been successfully
used as food additive for emulsifying and stabilizing oleoresin-
in-water emulsions (Vernon-Carter, Gómez, Beristaín, Mosqueira,
Pedroza-Islas, & Moreno-Terrazas, 1996; Vernon-Carter, Pedroza-
Islas, & Beristain, 1998), for entrapping water- and oil- soluble
colorants within water-in-oil-in-water multiple emulsions, which
in turn were converted into microcapsules (Rodríguez-Huezo,
Pedroza-Islas, Prado-Barragán, Beristain, & Vernon-Carter, 2004),
for microencapsulating and protecting Bifidobacterium bifidum
(Rodríguez-Huezo et al, 2007), for emulsifying and stabilizing orange
peel-oil emulsions (Román-Guerrero et al., 2009), for encapsulating
ferrous bisglycinate and releasing it from water-in-oil-in-water
multiple emulsions (Jiménez-Alvarado, Beristain, Medina-Torres,
Román-Guerrero, Vernon-Carter, 2009), and as a source of dietary
fiber in beverages (Beristain et al., 2006).
Calcium chloride, a divalent salt, has been incorporated into
coatings formulations to improve biopolymers cohesion
Silverson homogenizer (Silverson Machines, Ltd., Waterside, Che-
sham, Bucks., U.K.) operated at 10 000 rpm using a 50 mm
rotorestator generator for 5 min. Emulsions with a dispersed phase
mass fraction (4m) of 0.175 were obtained and coded according to
the aqueous solution from which they were obtained, thus result-
ing in two sets of emulsions: (1) MGCMOExCaCl2 , and
MGCMOEGlyxCaCl2 , where MG ¼ mesquite gum, C ¼ candelilla wax,
MO ¼ mineral oil, E ¼ emulsion, x ¼ percentage of CaCl2 in the
emulsion aqueous phase, and Gly ¼ glycerol. Glycerol was thus
added only to the emulsions labeled by MGCMOEGlyxCaCl2 . The
codes of all the emulsions are given in Table 1. All emulsions were
left to cool at room temperature before being characterized.
2.4. Determination of the average droplet size
A Malvern particle size and distribution analyzer series 2600
(Malvern Instruments, Ltd., Worcestershire, UK) was used to
determine the mean volume average droplet diameter (d30) by
applying the following general equation (Malvern Instruments,
Ltd., 1991):
"P # 1
Vi dm3
i
mn

(Mezgheni, D’Aprano, & Lacroix, 1998; Park, Rhee, Bae, &

d½m; n ¼ P (1)
Vi dn3
i
Hettiarachchy, 2001). Calcium ions act as a firming agent favoring
electrostatic interactions between two adjacent carboxylic groups, where Vi is the volume of droplets falling the ith droplet diameter
so that addition of calcium ions is likely to improve cohesion of MG- size (di), with both data sets provided by the instrument software.
based films as MG is a polyelectrolyte. This could probably lead to By making m ¼ 3 and n ¼ 0, d3,0 is obtained. All emulsions were
an enhanced entrapment and to a better protection for the analyzed in triplicate.
hydrophobic disperse phase.
The objectives of this work were to study the effect of adding
different concentrations of CaCl2, with or without the inclusion of 2.5. Calculation of the drop of coalescence of the emulsion droplets
glycerol as plasticizer, on: (1) the flow properties, mean droplet size
and stability of candelilla wax/mineral oil-in-mesquite gum emul- The rate of coalescence largely follows first-order kinetics
sions; and (2) the Atomic Force Microscopy surface morphology (Ye, Hemar, & Singh, 2004) and can be represented as
and the water vapor permeability (WVP) of the coatings casted
Nt
from the emulsions. ¼ eKc t (2)
N0
2. Materials and methods where Nt is the number concentration of droplets at time t, N0 is
the number concentration of freshly formed droplets (time ¼ 0),
2.1. Materials and Kc is the rate constant, which is related to the probability of the
interdroplet film (interfacial layer) rupturing in time t (Darling,
Mesquite gum (Prosopis laevigata) was hand collected in the 1987). When the volume of emulsion droplets remains constant,
form of tears in the Mexican State of San Luis Potosi, and purified that is, no oiling off occurs in the emulsions, the relationship
according to the method described by Vernon-Carter et al. (1996). between the emulsion droplet number, N, and the mean volume
Refined candelilla wax was provided by Ceras Deserticas, S.A. de C. average droplet diameter, d3,0, is given by (Sherman, 1969; Ye et al.,
V. (Mexico City, Mexico). Mineral oil (food grade) and glycerol were 2004)
purchased from Hycel de Mexico, S.A. de C.V. (Mexico City, Mexico).
Calcium chloride (CaCl2), sodium chloride (NaCl) and potassium
nitrate (KNO3) were from J.T. Baker, Inc. (Phillisburg, NJ). All the Table 1
Carreau-Yasuda rheological model parameters for the different emulsions.
water used in the experiments was double distilled.
Emulsion code Carreau-Yasuda rheological model parameters
2.2. Preparation of aqueous phase solutions h0hN hN l n a
(cP) (cP  109) (s) () ()
Two sets of mesquite gum aqueous solutions (10 g per 100 g of MGCMOE 1.63 1.50 30.63 0.42 8.11
distilled water) were prepared as structural materials: (1) one MGCMOE0:1 CaCl2 1.47 1.75 38.74 0.46 8.11
MGCMOE0:2 CaCl2 1.28 2.11 45.10 0.50 8.11
containing different concentrations of CaCl2 (0.0, 0.1, 0.2, 0.3, 0.4 or
MGCMOE0:3 CaCl2 0.99 1.46 46.38 0.49 4.92
0.5 g per 100 g); and (2) another one containing the same different MGCMOE0:4 CaCl2 0.64 1.59 37.67 0.54 8.11
concentrations of CaCl2 plus glycerol (1.5 g per 100 g). MGCMOE0:5 CaCl2 0.56 1.76 31.50 0.56 8.11

MGCMOEGly 0.64 1.32 7.03 0.41 8.11

2.3. Preparation of emulsions MGCMOEGly0:1 CaCl2 0.13 2.20 15.18 0.73 8.11
MGCMOEGly0:2 CaCl2 1.19 1.29 22.21 0.41 8.11
A blend of candelilla wax/mineral oil in a 2:1 ratio was heated at MGCMOEGly0:3 CaCl2 2.08 1.26 28.06 0.37 8.11
70
C and added dropwise to each of the aqueous phase solutions MGCMOEGly0:4 CaCl2 0.96 1.54 23.53 0.46 8.11
MGCMOEGly0:5 CaCl2 1.18 1.62 22.69 0.45 8.11
mentioned in Section 2.2, also at 70
C, with the help of a L4R
 E. Bosquez-Molina et al. / LWT - Food Science and Technology 43 (2010) 1419e1425 1421

square (rms) deviation of the heights of the various features imaged

 3
4 d3;0 by AFM as (Osés et al., 2009):
p N ¼ constant (3)
3 2 h . i0:5
The relative number of emulsion droplets can then be obtained rms ¼ Z21 þ Z22 þ . þ ZN2 N (5)
from (Ye et al., 2004)
where Zi are the height deviations from the data plane.
"  #3
Nt d3;0 t¼0
¼   (4) 2.9. Statistical analysis
N0 d3;0 t¼t
Statistical analysis of the droplet size, rate of coalescence and
If the kinetic plots of ln (Nt/N0) versus t for the emulsions give
water vapor permeability of the edible films was performed by
a straight line, then the slope is Kc.
analysis of variance (ANOVA) using the Statgraphics 7 statistical
analysis system (Statistical Graphics Corp. Manugistics Inc., Cam-
2.6. Emulsions flow properties bridge, MA). When it was pertinent significant differences
(P  0.05) between means were detected with Tukey’s test. All the
The viscosity-shear rate behavior of the emulsions was deter- experiments were done in duplicate.
mined with a modular compact rheometer (Physica, Model MCR
300) using a concentric cylinder measuring system, applying 3. Results and discussion
a shear rate from 0.05 to 100 s1 in a time interval of 5 min. The
temperature was maintained at 25
C with the help of a Peltier 3.1. Effect of Ca and glycerol on emulsion flow properties
system. Logelog plots of viscosity versus shear rate were analyzed
with different models (Casson, Carreau, Cross, CarreaueYasuda, The logelog plots of viscosity versus shear rate for all the
Power law) to determine which fitted best the experimental data. emulsions are shown in Fig. 1. All the emulsions displayed the
typical non-Newtonian behavior known as structural viscosity
2.7. Film forming and water vapor permeability determination (Darby, 1996). The experimental data of log viscosity versus log
shear rate were analyzed with several equations (Casson, Carreau,
Edible films were obtained by casting fifteen mL of candelilla Cross, CarreaueYasuda, Power law) that represent this type of
wax/mineral oil-in-solution mesquite emulsions on leveled teflon behavior. The model that best fitted the experimental data in all
plates using an 8-path square wet film applicator (Paul N. Gardner
Company, Inc., Pompano Beach, FL), which has on each side
a different under gap that allows for the casting of films of different
thickness. The gap employed was of 2 mm. Casting areas on the
plates were “framed” with layers of masking tape to restrain
solution spreading. The area casted was of 60 cm2. The spread
emulsions were dried by natural convection at ambient conditions
(25
C, 75e80% RH) for 24 h. The films were removed from the
plates using thin spatulas and immediately placed in an environ-
mental chamber (25
C and 50% RH) and held for 48 h before
testing. Circular samples of 10 mm were cut from each film and
a Mitutoyo digital micrometer (Mitutoyo Ltd., Tokio, Japan) was
used to measure film thickness to an accuracy of 0.001 mm.
Measurements were made at 10 random positions on each film
sample and an average value was calculated.
The water vapor permeability (WVP) of the edible films was
calculated using the ASTM Standard Method E-96-80 (ASTM, 1989),
known as the “cup method” and WVP correction method, respec-
tively, as described by Gennadios, Weller, and Gooding (1994).
Circular film samples of 10 mm diameter were placed over the
mouth of small cylindrical test cups. The arrangement of the
experimental unit employed and locations of water vapor partial
pressure values, relative humidity values and air gap heights were
the same reported by Bósquez-Molina et al. (2003). All tests were
carried out at 25
C, done by five replicates.

2.8. Atomic Force Microscopy

An atomic force microscope (Park Scientific Instruments, Model

Autoprobe CP) was used to examine the surface morphology of the
edible films in the contact mode. A sharpened Si3N4 cantilever with
a spring constant of 0.2 N m1 and a V-shaped tip 2 mm long was
positioned over the sample, and 80 mm  80 mm images were
obtained under ambient conditions. The AFM images provided
qualitative data (topographic images) as well as quantitative data
such as roughness. Roughness was calculated using root-mean
Fig. 1. Viscosity of mesquite gum based formulations with and without glycerol. CaCl2
was added to the emulsions within the range 0e0.5 g/100 g total emulsion. A
MGCMOE, - MGCMOE0.1Ca, : MGCMOE0.2Ca, , MGCMOE0.3Ca, D MGCMOE0.4Ca, C
MGCMOE0.5Ca (a) with glycerol, (b) without glycerol. Error bars indicate standard
deviation among three replications.
1422 E. Bosquez-Molina et al. / LWT - Food Science and Technology 43 (2010) 1419e1425

cases was the CarreaueYasuda rheological model (0.83  R2  0.98) Table 2

(Andrade, Petronílio, Maneschy, & Cruz, 2007): Initial mean volumetric droplet size d3,0 and rate of droplet coalescence of the
emulsions.

h  hN h  a iðn1Þ Emulsion code Initial mean volumetric Rate of coalescence

¼ 1 þ lg_
a
(6) (s1) of the emulsions
h0  hN droplet size d3,0 (SD)
of the emulsions (mm)
MGCMOE 1.67  0.01a 4.86 E-08a
This model describes pseudoplastic flow with asymptotic
MGCMOE0:1 CaCl2 1.70  0.01a 7.65 E-08b
viscosities at zero (h0) and infinite (hN) shear rates (g_), and with MGCMOE0:2 CaCl2 1.95  0.01b 8.13 E-08b
no yield stress. The parameter l is a constant with units of time, MGCMOE0:3 CaCl2 2.10  0.03c 8.66 E-09c
where 1/l is the critical shear rate at which viscosity begins to MGCMOE0:4 CaCl2 2.14  0.02d 4.86 E-08a
decrease. The power-law slope is (n-1) and the parameter MGCMOE0:5 CaCl2 1.95  0.12b 2.64 E-07d

a represents the width of the transition region between h0 and MGCMOEGly 1.72  0.09a 5.97 E-07a
the power-law region. The values of these five parameters for all MGCMOEGly0:1 CaCl2 1.97  0.07b 6.03 E-07a
MGCMOEGly0:2 CaCl2 2.14  0.01c 5.60 E-07a
the emulsions are given in Table 1. An inspection of these
MGCMOEGly0:3 CaCl2 2.55  0.01d 4.66 E-07b
parameters reveals that only l shows a clear-cut tendency, in that MGCMOEGly0:4 CaCl2 2.12  0.02c 4.42 E-06c
a maximum occurs for MGCMOE0.3Ca which exhibited a value of MGCMOEGly0:5 CaCl2 2.08  0.12c 7.85 E-06d
46.38 s (Table 1). Increasingly lower values for l were displayed Values are an average of three replications. Different letters in each row denote
by the formulations with other CaCl2 concentrations. As the significant difference at P < 0.05 (Tukey’s test).
concentration of CaCl2 increased or decreased further from 0.3 g
100 per g, so did the reduction in the value of l. This fact reveals
a great deal as to the effect of CaCl2 in the structuring of the
these films were considerably lower than their counterparts
mesquite gum based films. This typical viscosity characteristic of
without glycerol. Thus, it was inferred that the addition of glycerol
many non-Newtonian fluids (e.g. polymeric fluids, flocculated
to the films had an adverse effect in their structuring capacity,
dispersions, colloids) can be attributed to a reversible “structure”
probably due to the increased water holding capacity of the films
or network that forms in the “rest” or equilibrium state. When
containing glycerol, which contributed to a further dilution of the
the material is sheared, the structure breaks down, resulting in
polyions, increasing their “stiffness” and hindering their ability to
a shear-dependent behavior (Darby, 1996). A larger l value
interact.
signifies that the structure takes a longer time to break-down
Table 2 shows the initial mean volumetric droplet of the
when sheared or to reform when at rest, and implicitly, that
emulsions and their rate of droplet coalescence. A close inter-
a more interwoven or structured network was formed. Mesquite
relationship seems to exist among l, d3,0, and Kc. In the emul-
gum, which was used in this work as structural material, is
sions without glycerol, the largest initial droplet size was
a polyelectrolyte (Román-Guerrero et al., 2009; Vernon-Carter
displayed by MGCMOE0:4 CaCl2 , followed in descending order by
et al., 2000). Mesquite gum, due to the ionization of the
MGCMOE0:3 CaCl2 , MGCMOE0:2 CaCl2 , MGCMOE0:5 CaCl2 ,
attached function (eCOOHþ) readily solubilizes in water,
MGCMOE0:1 CaCl2 , and MGCMOE, respectively (Table 2). These
yielding a polyion and counterions. The polyion holds a large
results suggest that when the adsorbed mesquite gum molecules
number of charges in close proximity because they are attached
achieve a greater degree of “structuring” as indicated by l, the
to the macromolecules backbone. And although the polyion has
thickness of the adsorbed layer is greater, d3,0 larger, and the
mobility, the individual charges attached to the chain do not.
droplet coalescence kinetics is lower (see Table 2). The emul-
Additionally, not all of the counterions are free to move about.
sions incorporating glycerol showed the same tendency than
The free ions form a counterion cloud about the polyion, whereas
those without glycerol, but the mean initial droplet sizes were
the immobilized ions are bound to a specific site or point of the
larger, and the droplet coalescence rates higher (Table 2). These
macromolecular backbone. Expansion or dilution cannot occur
results indicate that when glycerol is combined with CaCl2,
indefinitely, due to flexibility constraints in the macromolecular
backbone. The more expanded the polyion, the higher is the
“stiffness” of the macromolecular backbone, so that the exposed
charged sites possess less freedom for interaction (Espinosa-
Andrews, Báez-González, Cruz-Sosa, & Vernon-Carter, 2007). Table 3
Thus, the MGCMOE emulsions exhibited the lowest l value (Table Effect of CaCl2 on the water vapor permeability and rms roughness of mesquite gum-
based edible films.
1) as the mesquite gum molecules were highly expanded and
their capacity to interact between themselves and other compo- Formulation Thickness WVP (g mm kPa1 rms roughness
nents was hindered. As CaCl2 was added to the formulations, (mm)  SD m2 d1)  SD (nm)  SD

shielding of the functional groups in the macromolecular back- MGCMOE 0.05  0.00a 88.05  2.45c 80.2  2.4
MGCMOE0:1 CaCl2 0.06  0.00a 75.76  2.37b,c 80.6  2.3
bone occurred, providing the macromolecular backbone with an
MGCMOE0:2 CaCl2 0.06  0.01a 63.22  1.98b,c 303.0  9.3
increasingly higher flexibility as CaCl2 concentration increased MGCMOE0:3 CaCl2 0.06  0.01a 52.03  2.05a 616.0  17.8
from 0.1 to 0.3 g per 100 g. It resulted in an increasingly struc- MGCMOE0:4 CaCl2 0.07  0.02a 66.97  1.89b 544.0  15.2
tured system (Table 1), in part due to the increasingly partici- MGCMOE0:5 CaCl2 0.07  0.00a 62.04  1.68b 323.0  10.0
pation of the Ca2þ in binding the intra- and intermolecular COO MGCMOEGly 0.07  0.02a 150.97  4.25e 108.0  3.1
functional groups of mesquite gum. However, as concentration of MGCMOEGly0:1 CaCl2 0.07  0.02a 152.42  5.13e 91.3  3.6
CaCl2 exceeded 0.3 g per 100 g, an excess of counterions occurred MGCMOEGly0:2 CaCl2 0.07  0.01a 160.27  4.65e 101.0  3.0
MGCMOEGly0:3 CaCl2 0.07  0.03a 141.11  3.21d 488.0  14.1
which shielded the charge of the functional groups, causing the
MGCMOEGly0:4 CaCl2 0.07  0.01a 165.26  4.87e 288.0  8.1
polyion to contract and offer fewer functional groups for inter- MGCMOEGly0:5 CaCl2 0.07  0.01a 155.15  3.93e 57.4  1.6
action. Thus, increasingly lower values for l were shown by
Thickness values are an average of ten replications, WVP values are an average of
MGCMOE0:4CaCl2 and MGCMOE0:5CaCl2 , respectively (Table 1). five replications, and roughness values are an average of measurements taken at five
The films incorporating glycerol in their formulation showed the different locations in the films. Different letters in each row denote significant
same general trend in the behavior of l, but the values exhibited by difference at P < 0.05 (Tukey’s test).
 E. Bosquez-Molina et al. / LWT - Food Science and Technology 43 (2010) 1419e1425
Fig. 2. 80 mm  80 mm AFM images of mesquite gum based films without glycerol: (a) MGCMOE, (b) MGCMOE0.1Ca, (c) MGCMOE0.2Ca, and (d) MGCMOE0.3Ca.
especially at concentrations above 0.3 g per 100 g, the Ca2þ ions
possibly achieve higher solubility and mobility, and that
shielding of the ionized carboxylic groups proceeds to a further
extent, decreasing the electrostatic repulsion term between
emulsion droplets.
3.2. Effect of Ca and glycerol on water vapor permeability (WVP)
According to the WVP values shown in Table 3, films with only
calcium showed significantly lower WVP values than the films with
glycerol and calcium. Furthermore, a close interrelationship seems
to exist among the WVP values displayed by the films and the
values of l and K shown by the emulsions from which they were
obtained. Higher coalescence rates can be associated to structural
matrices that were less dense and more open in the emulsions, and
perforce in the films, so that water vapor could diffuse more easily.
As CaCl2 concentration increased from 0.1 to 0.3 g per 100 g in the
coatings, WVP was significantly decreased, with the coatings dis-
playing denser structures that contributed to the increased WVP
barrier properties. Interactions between calcium and negatively
charged carboxyl groups in mesquite moieties could promote
bridging, leading to a more tightly knitted polysaccharide network
formation, impeding to greater extent moisture diffusion.
However, WVP was significantly increased as the concentration of
CaCl2 further increased to 0.4 and 0.5 g per 100 g in the coatings,
probably because an excess of Ca2þ counterions arose, shielding
the MG ionizable functional groups (COO Hþ), effectively
reducing the available moieties for interactions. As a result the
1423
polysaccharide- network weakened, displaying larger interstitial
spaces, facilitating water vapor diffusion.
3.3. Topography of edible films assessed by Atomic Force
Microscopy
The surface morphology of the mesquite gum matrices was
dependent on the CaCl2 concentration as observed from the AFM
images presented in Fig. 2 for films without glycerol. An impor-
tant feature of these micrographs is the film surface roughness.
The film made with pure mesquite gum (Fig. 2.a) presented the
smoothest surface, yet with a large amount of small circular
blisters, presenting a rms roughness of approximately 80 nm. The
film surface became increasingly rough as the CaCl2 concentration
increased from 0.1 to 0.3 g per 100 g (Fig. 2. b, c, d). Indeed, by
adding higher amounts of CaCl2 the number of blisters decreased
but their mean height increased, resulting in a higher rms
roughness. The maximum roughness, 616 nm, corresponded to
the film with 0.3 g CaCl2 per 100 g. Finally, this parameter
decreased for films with higher CaCl2 concentrations (0.4e0.5 g
per 100 g).
As shown in Fig. 3aed, the roughness for the films of MG with
glycerol also displayed a strong dependence on the CaCl2 content,
similar to the films without glycerol. The film without CaCl2 had the
smoothest surface, with a roughness of 108 nm. This parameter
then increased with CaCl2 addition up to 488 nm for the sample
with 0.3 g per 100 g (Fig. 2). The roughness for the sample with 0.5 g
per 100 g CaCl2 decreased to 57 nm.
1424 E. Bosquez-Molina et al. / LWT - Food Science and Technology 43 (2010) 1419e1425
Fig. 3. 80 mm  80 mm AFM images of mesquite gum based films with glycerol: (a) MGCMOEGly, (b) MGCMOEGly-0.1Ca, (c) MGCMOEGly-0.2Ca, and (d) MGCMOEGly-0.3Ca.
In short, it was found that CaCl2 addition contributes to increase
the structural material surface roughness, reaching a maximum
value for 0.3 g CaCl2 per 100 g, and that this roughness somehow
contributes to a better “coupling” of the structural material around
the lipophilic dispersed phase resulting in more compact films with
better properties against water vapor diffusion.
4. Conclusions
Films casted from emulsions with a 0.3 g CaCl2 per 100 g
concentration showed significantly lower WVP than those incor-
porating lower or higher CaCl2 concentrations or no CaCl2 at all. The
emulsions incorporating CaCl2 could be best described by the
YasudaeCarreau model. The parameter l varied with increasing
CaCl2 concentration, but achieved a maximum value at a concen-
tration of 0.3 g CaCl2 per 100 g, whether the formulation included
glycerol or not. Thus l provides a measure of the “structuring”
achieved by the emulsion. When l was maximum, the emulsion
droplet coalescence was minimum, and the water vapor perme-
ability of the films were minimum also. AFM images indicate that
the surface roughness of the films was affected by addition of CaCl2,
and the maximum surface roughness also occurred for 0.3 g CaCl2
per 100 g. A high surface roughness of the films possibly promotes
a better “coupling” of the “structural” material (mesquite gum)
around the dispersed oil phase (candelilla wax/mineral oil).
Acknowledgments
This work was partially financed by SNI-CONACyT. The authors
acknowledge the technical assistance of R. Fragoso and D. Jacinto.
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