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To cite this article: Rúben Pereira, Ana Tojeira, Daniela C. Vaz, Ausenda Mendes & Paulo Bártolo
(2011): Preparation and Characterization of Films Based on Alginate and Aloe Vera, International
Journal of Polymer Analysis and Characterization, 16:7, 449-464
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International Journal of Polymer Anal. Charact., 16: 449–464, 2011
Copyright # Taylor & Francis Group, LLC
ISSN: 1023-666X print=1563-5341 online
DOI: 10.1080/1023666X.2011.599923
Sodium alginate films with aloe vera extract were prepared by the casting/solvent evapor-
ation technique. The resulting films were characterized by differential scanning calorimetry,
Fourier transform-infrared spectroscopy, scanning electron microscopy, and mechanical
and water absorption tests. The in vitro degradation of the films was also investigated
over 14 days. Results show that aloe vera contributes to both enhancing the thermal
and mechanical properties of the films and decreasing the weight loss during in vitro
degradation.
INTRODUCTION
Over the years, there has been increasing interest in natural polymer–based
films, as they present a wide range of applications, especially in the food and phar-
maceutical industries.[1,2] In the food industry, natural polymers can be used as
protective coatings extending the life of food, thus improving food quality, while
in the pharmaceutical industry they can be applied as drug delivery systems or skin
dressings for wounds and burns. Alginate,[3] chitosan,[4] and cellulose[5] are com-
monly used for these purposes. Recently, the use of biopolymers in film preparation
has been increasing as an alternative to synthetic polymers, essentially due to their
availability, biocompatibility, relatively low cost, degradability, and nontoxic
properties.[6]
Sodium alginate is a water-soluble linear polysaccharide derived from
alginic acid, extracted from several species of brown algae, such as Laminaria
449
450 R. PEREIRA ET AL.
EXPERIMENTAL SECTION
Preparation of Sodium Alginate Solution and Aloe Vera Extract
Sodium alginate (Panreac Quı́mica, Spain) solutions at a concentration of 1.5%
(w=v) were prepared by dissolving 7.5 g of alginate in 500 mL of distilled water. The
solution was agitated in an orbital agitator incubator (Agitorb 200 IC, Aralab,
Portugal) for 24 h at a temperature of 25 C and a rotational speed of 180 rpm to
promote better uniformity. After this period of time, solutions were exposed to ultra-
sound for 30 min to remove air trapped bubbles. The aloe vera plant was provided by
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Viveiros de São Jorge, a Portuguese company. The leaves were washed with distilled
water to remove superficial contaminants, and the solutions were obtained by both
direct extraction of parenchyma leaves and subsequent grinding obtained under
controlled atmospheric conditions. The resulting suspension was filtered using a
vacuum filtration system with porosity ranging from 35 to 40 mm. The coarse
filtration allowed the removal of larger aloe vera fragments.
Film Preparation
Sodium alginate (SA) and sodium alginate=aloe vera (SA-Av) films were
prepared by casting=solvent evaporation. Before carrying out the deposition, both
solutions were mixed under constant stirring to promote the homogeneity of the final
solution. Afterwards, the solutions were put into a sonication bath to remove the
trapped air bubbles. SA films were then prepared by casting 15 mL and 20 mL of
SA solution into petri dishes (internal diameter of 95 mm). In order to prepare
SA-Av films, sodium alginate and aloe vera solutions were mixed in different propor-
tions to obtain final aloe vera amounts of 6% and 12% (v=v). The cast of mixed
solutions was performed to obtain films with two different thicknesses. The film
characteristics are indicated in Table I. The mixtures were cast onto petri dishes
using the same volumes of SA films. After drying at room temperature (25 C) for
a period of 72 h, the films were then removed from the petri dishes and conditioned
in desiccators prior to testing.
Considering the stability of gelified alginate-based films, the cross-linking effect
was evaluated in all films (SA II, SA-Av II, and SA-Av IV) by cutting circular sam-
ples 2 cm in diameter from each one and subsequently immersing them in 10 mL of
CaCl2 solution at 5% (w=v) for 15 min, allowing the alginate to cross-link. After this
period of time, the samples were removed and washed with distilled water and the
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excess water on the film surface was removed using filter paper. The influence of
the cross-linking in the samples was gravimetrically determined as a percentage of
the final weight and thickness relative to the initial weight and thickness.
Characterization of Films
Thickness. Film thickness was measured using a micrometer (Model 102-301,
Mitutoyo). Nine thickness measurements were taken along the length of the film.
The result, expressed by the mean of the measurements standard deviation (SD),
was used to evaluate the mechanical properties (tensile strength).
Moisture content. To determine the film moisture content, the samples were
weighed and then put into an oven at 110 1 C for 24 h. After this period of time,
the samples were conditioned in desiccators for 30 min for temperature stabilization.
Finally, the samples were weighed again, and the moisture content was determined
as a percentage of the initial film weight lost during drying, according to the
following equation:[13]
w1
Moisture content ¼ 100 ð1Þ
w0
where w1 corresponds to the dry weight of the film and w0 to the initial film weight.
All tests were performed in triplicate.
FT-IR analysis. FT-IR spectroscopy was used to identify both the film chemi-
cal structure and potential interactions between sodium alginate and aloe vera. The
FT-IR spectra of sodium alginate, aloe vera, and sodium alginate=aloe vera films
were obtained with a Nicolet Avatar 370 DTGS spectrometer (Thermo Electron
Corporation, Madison, Wis.). Lyophilized aloe vera sample and sodium alginate
powder were mixed with KBr powder and compressed into discs at a force of 7
kN for 2 min, using a manual tablet presser. For each spectrum, the measurements
FILMS BASED ON ALGINATE AND ALOE VERA 453
were performed in a range from 4000 to 400 cm1, with a resolution of 4 cm1.[4] All
samples were studied in triplicate.
Film morphology. The morphology of both the alginate and alginate=aloe
vera films was examined by a scanning electron microscope (Hitachi model
S2700), sputtering the samples with gold. SEM images were taken at an accelerating
voltage of 20 kV.
Mechanical properties. The evaluation of the aloe vera influence on the
mechanical properties of non-reticulated films was carried out with a Texturometer
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TA XT2i machine test (Dias de Sousa, Portugal). Film samples were cut into speci-
mens 15 mm wide and 50 mm long, following the guidelines of ASTM Standard
Method D 882.[19] The initial grip separation was 30 mm and the speed was 1 mm=s.
All samples were run three times. Results of the mechanical tests were expressed as
the mean of the measurements SD. Tensile strength (TS) was determined according
to the following equation:[4,9]
Fmax
TS ¼ ð2Þ
A
where Fmax and A represent, respectively, the maximum force at break and the initial
cross-sectional area of the film strip.
The elongation at break (E) was expressed according to the following
equation:[4,9]
L
E ð% Þ ¼ 100 ð3Þ
L0
where L corresponds to the difference in length at the rupture, and L0 represents the
initial length of the specimen.
Film water absorption. Water absorption tests were performed by immers-
ing the SA II, SA-Av II, and SA-Av IV cross-linking samples in 15 mL of 0.1 M HCl
(pH 2.2), phosphate buffer (pH 7.4), and distilled water (pH 5.2). The samples were
incubated inside an orbital agitated incubator at 37 C and 130 rpm.[20] At deter-
mined periods of time (10, 20, and 40 min), the swollen samples were withdrawn
and the excess water removed using filter paper. Afterwards, the samples were
immediately weighed (w1) and the water absorption ratio was determined as
follows:[20,21]
w1 w0
Water uptake ¼ 100 ð4Þ
w0
where w0 and w1 are the original and wet weight of the film samples, respectively.
Each test was performed in triplicate.
In vitro degradation tests. The in vitro degradation tests were carried out to
evaluate the influence of aloe vera on the degradation film profiles. In this test,
cross-linked SA-Av II and SA-Av IV films were used to study the degradation
454 R. PEREIRA ET AL.
kinetics, while the SA II film was used as a control. Pre-weighed dry specimens were
immersed in an isotonic saline solution (0.154 M sodium chloride solution, pH 5.6) at
37 C for 14 days. After predetermined periods of immersion (1, 3, 6, 9, and 14 days),
the samples were removed from the solution and dried inside a vacuum oven at 50 C
until constant weight was reached. The results were expressed as percentage of orig-
inal weight of the samples lost during the test, as a consequence of the dissolution=
degradation mechanisms. Tests were also performed in triplicate.
(SD). The comparisons between groups were performed used one-way analysis
of variance (ANOVA). A p value less than 0.05 was considered as indicative of
significance.
Figure 1. Transparent SA (a) and SA-Av (b) films (color figure available online).
FILMS BASED ON ALGINATE AND ALOE VERA 455
increase of all films due to water absorption, which demonstrates the uniformity of
the cross-linking process. However, the same behavior was not observed in the film
thickness. In this case, aloe vera seems to cause film dilatation, so there is an increase
in the samples’ diameter and a reduction of thickness.
Thermal Analysis
Table II summarizes the enthalpies, as well the endothermic and exothermic
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behavior associated with each peak temperature observed in the sodium alginate
powder, lyophilized aloe vera, and SA and SA-Av films.
Figure 2 shows the thermograms of unprocessed sodium alginate powder and
aloe vera. The sodium alginate thermogram shows two melting endothermic peaks
and one exothermic. The initial endothermic peak was observed at 82.8 C, while
the exothermic peak appears at 249.6 C. The aloe vera thermogram is characterized
by two endothermic peaks at 77.3 C and 172.9 C, with the first one presenting a high
enthalpy value. Endothermic peaks that appear at lower temperatures are probably
related to the transitions associated with the water loss of hydrophilic functional
polymeric groups,[6] while the exothermic peaks correspond to the polymer
degradation involving depolymerization and decomposition reactions.[6,18,22]
SA and SA-Av film thermograms are illustrated in Figure 3. In all cases, the
initial endothermic peaks correspond to lower temperature values than that of
unprocessed alginate. In the case of SA I and SA II films, the thermograms are very
similar, presenting one endothermic and one exothermic peak. Relative to the
Table II. Enthalpies and endothermic and exothermic behavior associated with each peak temperature
Temperature ( C)
Figure 2. Thermograms of sodium alginate powder (a) and aloe vera (b).
Figure 3. Thermograms of SA I (a), SA II (b), SA-Av I (c), SA-Av II (d), SA-Av III (e), and SA-Av IV (f)
films.
FILMS BASED ON ALGINATE AND ALOE VERA 457
volume used to produce the films, the results show that the highest volumes of
SA-Av II and SA-Av IV exhibit both a high exothermic peak temperature, respect-
ively 247.4 C and 249.2 C, and high enthalpy values, respectively 90.2 J=g and
100.7 J=g. The thermograms of SA-Av films exhibit a secondary endothermic peak
between 224.5 and 228.7 C, which can increase with the rise of the amount of aloe
vera, probably due to recrystallization, as well a phase transition of alginate after
heat induction, as stated by Pongjanyakul.[11] Regarding the influence of aloe vera
on the alginate films, the results show that the blending of alginate with aloe vera
causes a slight increase in the decomposition=degradation temperature of the films.
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These results seem to suggest that aloe vera contributes to the formation of a
more stable structure, probably due to stronger polymer-polymer interactions,
corresponding to a slight increase in film decomposition temperature.
Although several DSC analyses of alginate films were performed in previous
works,[6,11,18] no data have been reported until now relating the combination of aloe
vera extract with alginate films.
FT-IR Analysis
Spectroscopy tests were performed to detect either the appearance of new
chemical bonds or the modification of existing ones, which can be attributed to poss-
ible interactions between sodium alginate and aloe vera. The obtained spectra for
both sodium alginate and aloe vera are presented in Figure 4. Sodium alginate exhi-
bits absorption band characteristics at 3410 cm1, which can be due to hydroxyl
group (–OH),[10,11] 1635 cm1 (asymmetric stretching vibration of COO groups),
1419 cm1 (symmetric stretching vibration of COO groups), and 1050 cm1 (elonga-
tion of C-O groups).[3,10,18,22,23] In the case of the aloe vera spectrum, it was possible
Figure 4. FT-IR spectra of sodium alginate powder (a) and lyophilized aloe vera (b) (color figure available
online).
458 R. PEREIRA ET AL.
to identify absorption bands at 3427 cm1 and 1636 cm1, corresponding to the
OH stretching and asymmetric stretching vibration of COO groups, respectively.
Lyophilized aloe vera extract present a higher transmittance value than sodium
alginate powder.
Figure 5 shows the spectra of SA and SA-Av (I and III) films. SA film exhibits
a broader peak, ranging from 3543 to 3135 cm1, and other characteristic peaks at
1616 cm1, 1414 cm1, and 1036 cm1. The conversion of unprocessed alginate pow-
der into films caused an alteration on the band due to the hydroxyl group (3410 to
3543–3135 cm1) and shifted peaks at 1635 cm1, 1419 cm1, and 1050 cm1 to
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1616 cm1, 1414 cm1, and 1036 cm1, respectively. Incorporation of aloe vera at
6% (SA-Av I) produced a decrease on the absorption band of the hydroxyl group
(3477–3223 cm1), while the other peaks didn’t suffer significant alterations. The
incorporation of aloe vera at 12% (SA-Av III) increases the wavelength of the
characteristic absorption band of alginate, corresponding to the hydroxyl group
(3552–3111 cm1). Similarly, the peaks at 1616 and 1414 cm1 undergo an increase
to 1646 and 1416 cm1, respectively. Those changes correspond to good molecular
affinity between alginate and aloe vera. FT-IR tests suggest that alginate and aloe
vera probably establish chemical interactions, which is more evident for alginate
films with 12% of aloe vera.
Surface Morphology
Figure 6 presents the SEM images of SA I and SA-Av IV films without
cross-linking. Surface morphology of SA films is quite smooth and uniform, whereas
SA-Av films exhibits a rougher surface due to the presence of aloe vera. In the case of
SA-Av films, it is possible to identify aloe vera aggregates dispersed on the film
surface.
Figure 5. FT-IR spectra of SA I (a), SA-Av I (b), and SA-Av III (c) films (color figure available online).
FILMS BASED ON ALGINATE AND ALOE VERA 459
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Figure 6. SEM images of SA I (a) and SA-Av IV (b) films at 1000 of magnification; SA-Av IV film (c) at
5000 of magnification.
Mechanical Properties
Mechanical properties of SA and SA-Av films were evaluated regarding TS, E,
and Fmax. Results are presented in Table III.
Figure 7 shows the values of Fmax and TS for the tested films. From this figure,
it is possible to observe that the maximum force at break supported by the
Figure 7. Effect of film thickness and aloe vera concentration on the mechanical properties of SA and
SA-Av films. Data represent mean SD. P < 0.05 (color figure available online).
films increases with increase of aloe vera content. This result shows that aloe vera
contributes positively to the mechanical properties of the alginate films. In the
case of TS, it was observed that SA-Av films prepared through high solution
volumes result in lower thickness, and consequently low transversal section test,
exhibiting higher TS values. The obtained TS values range between
48.04 3.15 MPa and 59.46 1.12 MPa. Generally, SA-Av films show higher TS
values than SA films, highlighting the positive effect of aloe vera on the mechanical
properties. It is also possible to observe that aloe vera at 12% exhibits the maximum
force at break.
Relatively to the film elongation at break, the addition of aloe vera at 12% was
associated with a decrease in film elongation, suggesting that the enhancement of the
aloe vera content produces a more resilient, although more fragile (low elongation),
film. This behavior can be explained by the possible interaction established between
alginate and aloe vera, as suggested by FT-IR analysis. The interaction between
these compounds causes a decrease in the film’s elongation, but increases their
maximum force at break. Control films (SA I and SA II) exhibit a percentage of
elongation at break of 15.97 0.53% and 14.90 2.82% respectively, which is in
accordance with other works.[9,13] Alginate films with aloe vera content at 6% seem
to be the best solution, presenting better elongation values with satisfactory TS and
Fmax parameters.
Water Absorption
The water absorption test considers three different pH media by using a 0.1 M
HCl solution, distilled water, and phosphate buffer. It was observed that, in the case
of the phosphate buffer, the samples presented a high swelling degree in a short
period of time, causing their dissolution in consequence of ionic changes between
FILMS BASED ON ALGINATE AND ALOE VERA 461
the calcium ions present in the hydrogel structure and sodium ions, which are present
in the medium.
Figure 8 shows the water uptake of the films in 0.1 M HCl and distilled water at
different times. The results show that the film capacity to absorb water is dependent
on the pH value of the medium and the decrease of pH is associated with a decrease
in the films’ water uptake. As reported by Şanli and Solak,[21] alginate is protonated
into insoluble forms of alginic acid at lower pH values, which has an influence on the
swelling degree. The incorporation of aloe vera into the alginate films contributes to
a slight increase in the films’ water uptake for both HCl and distilled water media, as
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shown in Figure 8. In the case of the HCl medium, the films with aloe vera (SA-Av II
and SA-Av IV) exhibit equilibrium in water absorption after 20–40 min, while in
distilled water the equilibrium was not so evident. However, all samples immersed
in distilled water present higher values of water uptake.
Figure 8. Water uptake of the films in 0.1 M HCl (a) and distilled water (b). Data correspond to the
mean S.D., n ¼ 3 (color figure available online).
462 R. PEREIRA ET AL.
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Figure 9. Degradation profiles of the films. Data correspond to the mean S.D., n ¼ 3 (color figure
available online).
cross-link the alginate films) and sodium ions present in the isotonic saline
solution.[23]
CONCLUSIONS
Alginate films containing aloe vera at different proportions (6% and 12%) were
successfully prepared by the casting=solvent evaporation method, showing good
film-forming properties, transparency, and homogeneous surface. The physico-
chemical characterization of the prepared films showed that aloe vera contributes
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to increasing the thermal and mechanical properties of alginate films. These results
were corroborated by infrared spectroscopy analysis, which suggests the existence
of interactions between the alginate and aloe vera, especially at higher proportions
of aloe vera (12%). Regarding the water absorption and in vitro degradation tests,
the results indicate that aloe vera can contribute to a slight increase of the films’
water absorption capability, and simultaneously reduces film weight losses. The com-
bined data obtained through different tests allowed a better understanding of how
aloe vera influences the increase of alginate film properties, as well its potential to
be applied in such different fields as the biomedical, food, and pharmaceutical
industries.
REFERENCES
1. George, M., and T. E. Abraham. 2006. Polyionic hydrocolloids for the intestinal delivery
of protein drugs: Alginate and chitosan—A review. J. Control. Release 114: 1–14.
2. Tønnesen, H. H., and J. Karlsen. 2002. Alginate in drug delivery systems. Drug Dev. Ind.
Pharm. 28: 621–630.
3. Dong, Z., Q. Wang, and Y. Du. 2006. Alginate=gelatin blend films and their properties for
drug controlled release. J. Membr. Sci. 280: 37–44.
4. Khamhan, S., Y. Baimark, S. Chaichanadee, P. Phinyocheep, and S. Kittipoom. 2008.
Water vapor permeability and mechanical properties of biodegradable chitosan=methoxy
poly(ethylene glycol)-b-poly(e-caprolactone) nanocomposite films. Int. J. Polym. Anal.
Charact. 13: 224–231.
5. Phisalaphong, M., and N. Jatupaiboon. 2008. Biosynthesis and characterization of
bacteria cellulose-chitosan film. Carbohydr. Polym. 74: 482–488.
6. Zohuriaan, M. J., and F. Shokrolahi. 2004. Thermal studies on natural and modified
gums. Polym. Test. 23: 575–579.
7. Rezende, R. A., P. J. Bártolo, A. Mendes, and R. Maciel Filho. 2009. Rheological beha-
vior of alginate solutions for biomanufacturing. J. Appl. Polym. Sci. 113: 3866–3871.
8. Ashikin, W., T. W. Wong, and C. L. Law. 2010. Plasticity of hot air-dried mannuronate-
and guluronate-rich alginate films. Carbohydr. Polym. 81: 104–113.
9. Rhim, J.-W. 2004. Physical and mechanical properties of water resistant sodium alginate
films. Lebensm. Wiss. Technol. 37: 323–330.
10. Han, J., Z. Zhou, R. Yin, D. Yang, and J. Nie. 2010. Alginate-chitosan=hydroxyapatite
polyelectrolyte complex porous scaffolds: Preparation and characterization. Int. J. Biol.
Macromol. 46: 199–205.
11. Pongjanyakul, T. 2009. Alginate-magnesium aluminum silicate films: Importance of
alginate block structures. Int. J. Pharm. 365: 100–108.
12. Murakami, K., H. Aoki, S. Nakamura, S.-I. Nakamura, M. Takikawa, M. Hanzawa, S.
Kishimoto, H. Hattori, Y. Tanaka, T. Kiyosawa, Y. Sato, and M. Ishihara. 2010. Hydrogel
464 R. PEREIRA ET AL.
The efficacy of aloe vera used for burn wound healing: A systematic review. Burns. 33:
713–718.
16. Vogler, B. K., and E. Ernst. 1999. Aloe vera: A systematic review of its clinical effective-
ness. Br. J. Gen. Pract. 49: 823–828.
17. Boudreau, M. D., and F. A. Beland. 2006. An evaluation of the biological and toxicologi-
cal properties of Aloe barbadensis (Miller), aloe vera. J. Environ. Sci. Health C Environ.
Carcinog. Ecotoxicol. Rev. 24: 103–154.
18. Sarmento, B., D. Ferreira, F. Veiga, and A. Ribeiro. 2006. Characterization of
insulin-loaded alginate nanoparticles produced by ionotropic pre-gelation through DSC
and FTIR studies. Carbohydr. Polym. 66: 1–7.
19. American Society for Testing and Materials. 2002. ASTM D 882. Standard test methods
for tensile properties of thin plastic sheeting. In Annual Book of ASTM Standards, vol.
06.01, pp. 164–173. West Conshohocken, Penn.: American Society for Testing and
Materials.
20. Pongjanyakul, T., and S. Puttipipatkhachorn. 2007. Alginate-magnesium aluminum
silicate films: Effect of plasticizers on film properties, drug permeation and drug release
from coated tablets. Int. J. Pharm. 333: 34–44.
21. Şanli, O., and E. K. Solak. 2009. Controlled release of naproxen from sodium alginate and
poly(vinyl alcohol)=sodium alginate blend beads crosslinked with glutaraldehyde. J. Appl.
Polym. Sci. 112: 2057–2065.
22. Mimmo, T., C. Marzadori, D. Montecchio, and C. Gessa. 2005. Characterisation of Ca-
and Al-pectate gels by thermal analysis and FT-IR spectroscopy. Carbohydr. Res. 340:
2510–2519.
23. Bajpai, S. K., and S. Sharma. 2004. Investigation of swelling=degradation behaviour of
alginate beads crosslinked with Ca2þ and Ba2þ ions. React. Funct. Polym. 59: 129–140.