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Rheological and structural characterization of prepared aqueous

Aloe vera dispersions


Patruni Kiran, P. Srinivasa Rao
Agricultural and Food Engineering Department, Indian Institute of Technology Kharagpur, Kharagpur-721302, West Bengal, India
a b s t r a c t a r t i c l e i n f o
Article history:
Received 22 December 2013
Accepted 19 May 2014
Available online 28 May 2014
Keywords:
Aloe barbadensis Miller
Powders
A. vera dispersions
Rheology
Crossover points
The rheological and structural properties of prepared aqueous dispersions from Aloe vera brous and the non-
brous powders were investigated. Flow behavior of the dispersions of freeze dried (FD), dehumidied air
dried (DH), and hot air dried (HA) brous powders and the non-brous alcohol insoluble residues (NFAIR)
have been investigated at different temperatures of 30, 40, 50, and 60 C as well as concentrations of 0.2, 0.4,
0.8, 1.6 and 3.2% (w/v). The prepared dispersions exhibited shear thinning behavior based on power law
model. Functional groups identication in the powders was performed by FTIR spectroscopy and the presence
of bioactive acetyl groups was conrmed from the study. Dynamic oscillatory analyses of concentrated
dispersions were also carried out at a critical volume. Fibrous dispersions showed low critical volume (1.5 to
2.5 mL H
2
O/100 mg of dry matter) and 1000 times higher magnitude of elastic modulus (G) (12,320 to
32,043 Pa) than fresh juice (2 to 25 Pa) indicating a solid like property (G N G) throughout the frequency
range. On the other hand, the non-brous powder showed a high critical volume (10 mL H
2
O/100 mg of dry
matter) with water and crossover points (G = G at frequency 0.801 Hz) depicting its solgel behavior.
2014 Published by Elsevier Ltd.
1. Introduction
Aloe vera L. (syn. Aloe barbadensis Miller) is a medicinal plant belong-
ing to the family Liliaceae. It is widely used in a variety of food applica-
tions, cosmetics and pharmaceutical industries (Eshun & He, 2004;
Rodriguez Rodriguez, Darias Martin, & Diaz Romero, 2010). Aloe vera
L. (A. vera) mainly contains both nutritious and non-nutritious portions
(Rodriguez Rodriguez et al., 2010). Physical and biochemical properties
of A. vera gel has been well characterized (Femenia, Garca-Pascual,
Simal, & Rossell, 2003; Femenia, Snchez, Simal, & Rossell, 1999)
and extensively investigated (Ni, Turner, Yates, & Tizard, 2004;
Rodrguez-Gonzlez et al., 2011; Sharrif & Sandeep, 2011). The plant
posses bioactive polysaccharides such as acemannan, glucomannan,
pectin and aloeride responsible for diverse biological activities such as
immunomodulatory, anti-inammatory, anti-diabetic, anti-cancerous
etc (Ahlawat & Khatkar, 2011; Ramachandra & Rao, 2008). Apart from
controlling the chemical, functional and physical properties of native
A. vera gel and juice are still a major challenge for its processing. It is
due to the microbial, mechanical, enzymatic and structural alterations
that happen during different climatic and processing conditions
(Ahlawat & Khatkar, 2011; Femenia et al., 1999; He, Changhong, Kojo,
& Tian, 2005; Ramachandra & Rao, 2008). Therefore, several studies
have been carried out targeting the cost-effective production of A. vera
powder fromcrude llet (A. vera parenchyma) by optimizing the differ-
ent drying methods such as hot-air drying, dehumidied air drying, and
freeze drying. (Chakraborty, Bera, Mukhopadhyay, & Bhattacharya,
2011; Ramachandra & Rao, 2009; Simal, Femena, Llull, & Rossello,
2000). On the other hand, the isolation of A. vera pulp into partially
puried pulp based products was also studied due to the presence of
bioactive acetylated polysaccharide within it (Ni et al., 2004).
Knowledge on rheological properties is necessary prior to the prod-
uct formulation for understanding structural and functional properties
of food products. In recent years, rheological studies of prepared
A. vera gel/solutions from powder covered both ow and deformation
behaviors. Flow analysis helps to distinguish the Newtonian and Non-
Newtonian behavior of uid. Deformation analysis helps in understand-
ing viscoelastic behavior of samples without any structural alteration.
Rheological behavior of A. vera mainly depends on parameters such as
presence of insoluble bers, bioactive acetyl groups, processing condi-
tions, polymeric concentration, and temperature. Frequency sweep
and ow curves on native A. vera gel and juice have been reported to
show that the elastic modulus of A. vera gel dominated over A. vera
juice and also showed shear thinning behavior (Lad & Murthy, 2013).
The weak network between insoluble ber and the polysaccharides in
A. vera gel was mainly responsible for their micro-structural and rheo-
logical changes. On the other hand, method of drying had shown signif-
icant effect on the viscosity () and glass transition temperature (T
g
) of
Food Research International 62 (2014) 10291037
Corresponding author at: Agricultural and Food Engineering Department, Indian
Institute of Technology, Kharagpur, West Bengal 721302, India. Tel.: +91 3222
283164; fax: +91 3222 282244.
E-mail addresses: patrunikiran@agfe.iitkgp.ernet.in (P. Kiran),
psrao@agfe.iitkgp.ernet.in (P.S. Rao).
http://dx.doi.org/10.1016/j.foodres.2014.05.033
0963-9969/ 2014 Published by Elsevier Ltd.
Contents lists available at ScienceDirect
Food Research International
j our nal homepage: www. el sevi er . com/ l ocat e/ f oodr es
A. vera solutions prepared from dried powders reconstituted to 87%
moisture content (Nindo, Powers, & Tang, 2011). In A. vera pectin-
calcium hydrogel, the in situ gelling mechanism and Ca
2+
cross-
linking concept has been earlier demonstrated (McConaughy,
Kirkland, Treat, Stroud, & McCormick, 2008; McConaughy, Stroud,
Boudreaux, Hester, & McCormick, 2008). A. vera pectin was used for
nasal drug release as they were showing the steady state ow and
also gel to sol behavior during frequency sweep. The effect of concentra-
tion dependent frequency sweep in aqueous solution prepared from
A. vera extract (AE) and the polysaccharide fraction (PF) has been inves-
tigated (Campestrini, Silveira, Duarte, Koop, & Noseda, 2013).
Despite of extensive research works in A. vera powder formation,
there is scanty information available on the structural and rheological
changes in the aqueous A. vera dispersions prepared from whole llet
powders (brous) and the partially puried (non-brous alcohol insol-
uble residue) powder. It is also crucial to understand the role of concen-
tration and temperature in prepared aqueous dispersions on the
rheological behavior, not only from commercial point of view but also
to develop products with desired functionalities and enhanced stability.
The theoretical concepts were established in the case of homogeneous
suspensions (Citerne, Carreau, & Moan, 2001), but for complex hetero-
geneous suspensions limited literatures are available as the material be-
havior is governed by the concepts, such as hydrodynamic, Brownian
and collisions forces between the particles (Genovese, Lozano, & Rao,
2007), and it is alsovery difcult to predict the role of individual compo-
nents on rheology (Lad & Murthy, 2013).
The study aims to evaluate the functional and micro-structural char-
acteristics of the brous (FD, HA, DH) and non-brous (NFAIR) A. vera
powders by FTIR and SEMtechniques. Further, the owand viscoelastic
behaviors of prepared aqueous A. vera dispersions have also been
studied.
2. Materials and methods
2.1. Preparation of A. vera brous and non-brous powder
The llet brous A. vera powders were prepared by different drying
methods at optimized conditions, such as freeze dried (FD) powder pre-
pared at 40 C (Ramachandra & Rao, 2008), dehumidied air dried
(DH) powder obtained by drying at 54 C (Ramachandra & Rao, 2009),
and hot air dried (HA) powder by drying at 40 C (Ramachandra &
Rao, 2009). The non-brous alcohol insoluble residue (NFAIR) powder
was also prepared as described by Ni et al. (2004), with slight modica-
tion. In brief, A. vera pulp was subjected to centrifugation at 10,000 rpm
for 30 min and bers were separated fromthe residue. The supernatant,
which includes both micro-particle and liquid gel, was subjected to alco-
hol precipitation (sample:ethanol = 1:3 v/v). The resulting precipitate
was collected and freeze dried.
2.2. Estimation of total polysaccharide content
The total polysaccharide content in A. vera fresh (brousFJ, and
clearCJ) juices, whole llet powders (FD, DH, and HA), and NFAIR
was estimated by phenol-sulphuric acid method. The samples' absor-
bance was determined by UV spectrophotometer (UV-1700, Shimadzu,
Japan) at 490 nm. Total polysaccharide content was calculated fromthe
standard curve generated from D (+) glucose analysis (Vega-Glvez
et al., 2012). Polysaccharide analysis was performed in duplicate and
measured in triplicate, and the respective mean values were reported.
2.3. Fourier transform infrared spectroscopy (FTIR)
The FTIR spectra for A. vera powders were measured in the frequen-
cy range from 400 to 4000 cm
1
by using spectrometer (Nicolet 6700,
Thermo Scientic, Madison, WI, USA). The dried powders were ground
with KBr powder and pressed into pellets for FTIR spectra measurement
(Nejatzadeh-Barandozi & Enferadi, 2012).
2.4. Scanning electron microscopy (SEM)
The A. vera powders were mounted on a circular aluminum speci-
men stub and gold-coated in a vacuum environment by using sputter
coater to form conducting surface. The A. vera granular structures of -
brous (FD, HA, and DH) powders were examined by transferring the
specimen to scanning electron microscope at 1000 magnication
(JSM5800, JEOL, Japan). Comparison of brous (FD) and non-brous
(NFAIR) powders was done at 500 magnication (EVO 60, Carl ZEISS
SMT, Germany).
2.5. Preparation of aqueous A. vera dispersions for rheological analysis
Aqueous dispersions were prepared from dried brous and non-
brous powders at desired concentrations of 0.2, 0.4, 0.8, 1.6, and 3.2%
(w/v). The dispersions were subjected to mild heating and stirring for
partial dissolution of heterogeneous compounds in the powder. The
prepared samples were equilibrated at room temperature for 24 h
prior to dynamic viscosity analysis where the fresh A. vera brous (FJ)
and clear (CJ) juices were taken as control.
Concentrated aqueous dispersions were prepared by dissolving
100 mg powder in 1.52.5 mL distilled water depending upon different
critical volumes. The critical volume was estimated by crude test tube
tilting (TTM) method (Haghighi & Rezaei, 2012; Pal, Shrivastava, &
Dey, 2009), where the volume of the dispersion was considered, when
meniscus did not ow or deform due its own weight. Tilting test was
performed in duplicates and the measured values were expressed as
their respective mean. The samples were equilibrated at room temper-
ature for 24 h prior to viscoelastic analysis. Further visual inspections
were carried out for both concentrated and dilute dispersions.
2.6. Rheological measurements and analysis
The rheological measurements were performed in a stress
controlled rheometer (Bohlin Gemini 200, Malvern Instruments Ltd.,
Malvern, UK). Controlled shear rate measurements were performed
using cup and bob (C25 DIN 53019). To prevent the evaporation of the
solvent, the free surface of the sample was always covered by solvent
evaporation trap. Sample temperature was controlled by Peltier
unit connected with a circulating water bath and software (Bohlin
R6.51.0.3) was used for data acquisition. A sample of 10 mL was loaded
into the cylinder and was allowed to equilibrate to maintain set temper-
ature and applying shear rate from0.1 to 100 s
1
. The owbehaviors of
A. vera dilute dispersions juice were analyzed at different temperature
of 30, 40, 50, and 60 C and different concentrates of 0.2, 0.4, 0.8, 1.6
and 3.2% (w/v). Experimental data were evaluated and tted according
to the rheological model Power Law (Eq. (A.1)).

n
A:1
Dynamic oscillatory measurements were carried out for concentrat-
ed dispersions at critical volume equippedwitha parallel plate diameter
of 20 mm (PP-20). Amplitude sweep experiment was initially per-
formedat frequency 1 Hz, for the minimumand maximumstress ranges
(specic to sample) to detect linear viscoelastic region(LVR). Frequency
sweep test was conducted at 25 C in a frequency range from 0.1 to
10 Hz at constant stress selected from LVR zone. Dispersion samples of
2 mL were carefully placed on the lower plate, where the gap between
two plates was 1000 m. The samples were stabilized with an initial
equilibrium time of 30 s before the oscillation started. The viscoelastic
behavior of the samples was characterized by two mechanical
1030 P. Kiran, P.S. Rao / Food Research International 62 (2014) 10291037
responses: elastic modulus (G) (Eq. (A.2)), and viscous modulus (G)
(Eq. (A.3)).
G
0


0

0
cos A:2
G

0
sin A:3
In this
0
indicates the initial stress (in Pa),
0
indicates the initial
strain (s
1
) and indicates phase angle
3. Results and discussion
3.1. Total polysaccharides content in brous and non-brous residues
The variation in total polysaccharide content of different A. vera
powders has been shown in Fig. 1A. The average total polysaccharide
contents in FD, DH and HA powders were 39, 34, and 31% (w/w) of
dry matter, respectively (Table 1). It indicated that the methods of dry-
ing had least impact on the total polysaccharides content, and similar
results were obtained for other drying methods by Nindo et al. (2011).
Although, the net amount of polysaccharide was almost similar to FD,
it was observed that DHincomparisonto HApresentedincreasedreten-
tion. NFAIR showed low polysaccharide content such as 18% (w/w)
of dry matter. It might be due to the discarding of the residue after
centrifugation prior to alcohol treatment in which some cell wall
polysaccharides, such as cellulose, and hemicelluloses had also been
lost (Ni et al., 2004; Yaron, Cohen, & Arad, 1992). However, fresh
juices (FJ and CJ) showed high polysaccharide content such as 55 and
48% (w/v) of dry matter. Similar results had been reported earlier
(Lad & Murthy, 2013; Swami Hulle, Patruni, & Rao, in press). But as
cited above, percentage of total polysaccharide content was different
from the obtained results as it highly depends on initial processing,
method of drying, climatic conditions, hydrophobic, hydrophilic and
components as well as solvent.
3.2. FTIR analysis
The presence of functional groups in non-brous powder and the ef-
fects of drying methods on the crude brous powder were analyzed by
FTIR. The results were compared with the existing reports related to cell
wall polysaccharides, puried bioactive polysaccharide fractions as well
as methanol extracted phenolics fraction for validation purpose
(Kacurakova, Capek, Sasinkova, Wellner, & Ebringerova, 2000;
Nejatzadeh-Barandozi & Enferadi, 2012; Ray & Aswatha, 2013; Ray,
Dutta Gupta, & Ghosh, 2013; Rodrguez-Gonzlez et al., 2011; Swami
Hulle et al., in press).
FTIR prole in different A. vera powders indicated the presence of
\OH (corresponds to 3420 cm
1
), \CH stretching (corresponds to
2923 cm
1
), C_O stretches of acetyl (corresponds to 1760
1740 cm
1
), C_O (corresponds to 16501578 cm
1
), COO\
asymmetric stretching (corresponds to 1598 cm
1
), CH
3
and
COO\ symmetric stretching (corresponds to 1428 cm
1
), C\O\C
stretches of acetyl groups (corresponds to 1248 cm
1
), ether
C\O\C in sugar (corresponds to 10911030 cm
1
), and glucan
Fig. 1. Variation in A) total polysaccharides content and B) critical volume of different A. vera powders.
Table 1
Total polysaccharide, critical volume andcritical stress values for fresh juices and prepared aqueous A. vera dispersions (brous and non-brous) (average andstandarddeviation values of
3 measurements).
Sample A. vera powder Total polysaccharide Critical volume Critical stress
Average Stdev. Average Stdev. Average Stdev.
FJ 55 5.5 NA NA 000.11 0.05
CJ 48 3.5 NA NA 000.04 0.01
FD 39 2.2 02.5 0.13 365.00 0.03
DH 34 0.7 01.5 0.14 147.00 0.02
HA 31 1.4 02.0 0.08 082.00 0.20
NFAIR 18 2.1 10.0 0.71 010.00 0.02
1031 P. Kiran, P.S. Rao / Food Research International 62 (2014) 10291037
bands (corresponds to 1031 cm
1
). Strong and broad intensity of
the peaks at 3420 cm
1
conrmed the presence of hydroxyl group
which also indicated the presence of moisture, as reported by several
researchers (Kacurakova et al., 2000; Nejatzadeh-Barandozi &
Enferadi, 2012).
FTIR spectrum of the crude llet powder showed the presence of
heterogeneous structure due to intermediate peaks. FD powder
absorbance bands were seen in the range of 17601740 cm
1
and
1248 cm
1
which attributed to C_O and C\O\C stretching of acetyl
groups present in the sample (Fig. 2A). The presence of acetyl groups,
which mainly contain hydrophilic hydroxyl groups, helps in promoting
the biological activity and also is responsible for the passage throughthe
hydrophobic cell barrier (Reynolds & Dweck, 1999). However, bands in
the range of 17601740 cm
1
and 1248 cm
1
intensity decreased in
case of DHpowder followed by HApowder indicating the minor content
of acetyl groups. Moreover, the bands at 16501578 cm
1
implied the
presence of C_O stretching and indicated the presence of carboxyl
components and phenolic compounds which are polar in nature
(Kacurakova et al., 2000; Ray & Aswatha, 2013; Ray et al., 2013). FTIR
spectrum of NFAIR was mainly compared with the polysaccharides re-
ported so far (Fig. 2B) (Ni et al., 2004). The absorbance spectrum at
around 1740 cm
1
, 1598 cm
1
, and 1248 cm
1
can be accounted to
the presence of C_O, COO\, and C\O\C stretches of acetyl groups,
and results were in agreement with the bioactive acetylated
Fig. 2. FTIR spectra of A) brous (FD, DH, and HA), B) non-brous (NFAIR) A. vera powders.
Fig. 3. Scanning electron micrograph images of A. vera brous powders (1000 X) A) FD, B) DH, C) HA, and brous and non-brous (500 X) 4) FD, 5) NFAIR powders.
1032 P. Kiran, P.S. Rao / Food Research International 62 (2014) 10291037
polysaccharide as reported earlier (Rodrguez-Gonzlez et al., 2011;
Swami Hulle et al., in press; Yaron et al., 1992). The identication of
strong bands in the range of 10781036 cm
1
is most pronounced
due to the presence of polysaccharide sugars, such as galactose and glu-
cans in accordance with the previous studies (Nejatzadeh-Barandozi &
Enferadi, 2012). The presence of acetyl groups and partial acetylated
4-linked -D-glucomannan was also conrmed by NMR techniques as
reported earlier (Campestrini et al., 2013).
3.3. SEM observations
Structural alteration during drying and solvent treatments within
the A. vera powder was characterized with the help of scanning electron
microscope (SEM). The intact cell structure throughout the sample, as
observed in FD powder (Fig. 3A), indicates the presence of cell wall
polysaccharides in which cellulose is responsible for strength and stiff-
ness, and pectin gives the plasticity (Miranda et al., 2010). However,
the irregular cell structure with amorphous surface was observed in
DH and HA (Fig. 3B and C), which might be due to the loss of other
cell wall polysaccharides such as pectinacious material without affect-
ing the cellulose (Vega-Glvez et al., 2011). Further, FD and NFAIR sam-
ple showed the presence of brous laments and non-brous rough
intact surface at 500 magnication. It implied that, elimination of -
bers affected the surface morphology of cell wall membrane polysac-
charide due to degradation of pectinacious substances during A. vera
juice processing (as shown in Fig. 3D and E).
3.4. Visual inspection of prepared dispersions
Visual inspection of aqueous A. vera dispersions (brous and non-
brous) showed that the brous fractions were settling down at the
bottom of the test tube (Fig. 4) which might be due to the presence of
insoluble cellulose (Lad & Murthy, 2013; Moelants et al., 2013). The
lower concentration of non-brous fraction was soluble in nature and
it formed gel like networks at higher concentration indicating its suit-
ability for hydrogel formation which might attribute to the presence
of partially soluble bioactive acetyl polysaccharides (Campestrini et al.,
2013). The obtained results suggested that brous dispersions at de-
sired concentration might be suitable to recover its consistency
(Nindo et al., 2011) and the dispersion was submitted for further ow
analysis. However, the comparison of the concentration effects among
brous dispersions on the deformation was difcult as there was a
clear separation between solvent and dispersed phase. Moreover, non-
brous dispersions were found to be suitable for both ow and oscilla-
tion analysis at selected concentrations due to the uniform distribution
in solvent and their partial solubility in aqueous medium.
Dynamic oscillation study was conducted for comparing both -
brous and non-brous dispersion at a critical volume concentration
where the separation of solvent and dispersed phase was absent for
boththe cases (Fig. 4C). The variationincritical volume of A. vera disper-
sions of all brous powders and the gel prepared fromnon-brous pow-
der (NFAIR) is presented in Fig. 4A and B. The whole llet powders
showed critical volume in the range of 1.5 to 2.5 mL H
2
O/100 mg of
dry matter (dm) (Table 1), depicting the presence of heterogeneous
cell wall polysaccharide networks which prevent the H-bond formation
with aqueous environment. The critical volume values for HA and DH
samples were lower compared to FD. It might be due to the breakdown
of cell wall polysaccharide during drying treatment. However, the ob-
tained critical volume in case of NFAIR powders was in higher side
(10 mL H
2
O/100 mg of dry matter). It might be attributed to the fact
that discarding the hydrophobic cellulose portion after centrifugation
may lead to availability of the spacious substituent's which helps in sol-
vent penetration and additional network formation.
3.5. Flow behavior of prepared brous/non-brous aqueous dispersions
Power law model (Eq. (A.1)) showed best t for both brous (FD)
and non-brous (NFAIR) dispersions (R
2
N 0.88) with an exception for
non-brous powder at 0.4% w/v and 40 C where R
2
= 0.69. As expect-
ed, the higher concentrations and lowtemperature conditions helped in
promotion of viscosity of the dispersions (Table 2) which might be due
to the inuence of internal bond formation. Flow behavior index (n)
Fig. 4. Visual images of prepared aqueous A. vera dispersions of A) FD, B) NFAIR and C) FD and NFAIR at critical volume.
1033 P. Kiran, P.S. Rao / Food Research International 62 (2014) 10291037
values for all samples varied in the range of 0.100.80 demonstrating
the shear thinning behavior (n b 1). In Fig. 5A, value of all samples de-
creases withincrease intemperature, as expected, reasonmight be loos-
ening of the polymeric networks present in the sample, and similar
characteristics have also been reported (Lad & Murthy, 2013; Nindo
et al., 2011; Swami Hulle et al., in press). Further, FJ showed higher
value than CJ at 3060 C. Increase in values might be due to the pres-
ence of intermingled brous clusters, which interacted with surround-
ing liquid constitutes of other polymeric chains (Lad & Murthy, 2013;
Tatsumi & Matsumoto, 2007). However, in prepared aqueous disper-
sions, the values were in the order of FD N NFAIR N HA N DH at 30
60 C. Drying techniques affected the polysaccharide content which al-
tered the morphology of the pectinacious substances responsible for
plasticity (as described in SEM) of the powders which in turn govern
the rheology (Nindo et al., 2011). Interestingly, the viscosity in NFAIR
was due to exposure of high molecular weight bioactive acetyl groups
(as demonstrated in FTIR) by removal of the cell wall hydrophobic moi-
ety, which further participated in solvent penetration by hydrogen and
hydrophobic interactions (Campestrini et al., 2013).
In Fig. 5B, the values were in higher side ( in the range of 0.059 to
0.099 Pas) for fresh A. vera juices (both FJ and CJ) at 30 C at 100 s
1
compared to aqueous dispersions at concentrations 0.21.6% (w/v) (
varies from 0.001 to 0.026 Pas) prepared from powders. However, at
3.2% (w/v), value found to be increased (in the range of 0.022 to
0.164 Pas) for brous (FD) and non-brous (NFAIR) than fresh juice.
The viscosity of dispersions prepared from DH and HA at 3.2% (w/v)
was lowest due to disruption of polysaccharides networks. In FDdisper-
sions, increase in concentration promoted the interaction among the
random and weak polymeric clusters with surrounding liquid contain-
ing soluble polymeric chains (Lad & Murthy, 2013; Tatsumi &
Matsumoto, 2007). In NFAIR dispersions, the increase in concentrations
might have helped in promotion of additional hydrogen, hydrophobic
Table 2
Power law model parameters for fresh juices (FJ and CJ) and prepared aqueous A. vera brous (FD) and non-brous (NFAIR) dispersions at different concentrations and temperatures
(average and standard deviation values of 3 measurements).
Sample Temp. (C) R
2

2
(Pas) n
FJ 30 0.987 5.040 2.906 0.086 0.264 0.028
40 0.983 4.320 2.454 0.094 0.285 0.015
50 0.981 10.29 1.320 0.085 0.416 0.032
60 0.982 0.864 1.124 0.036 0.419 0.042
CJ 30 0.970 5.322 0.320 0.050 0.630 0.009
40 0.990 1.482 0.125 0.045 0.761 0.020
50 0.990 0.653 0.093 0.075 0.786 0.021
60 0.990 0.171 0.062 0.058 0.813 0.026
FD concentration Temp. (C) R
2

2
(Pas) n
0.2 30 0.959 0.635 0.048 0.010 0.559 0.020
40 0.904 0.917 0.029 0.006 0.588 0.030
50 0.932 0.169 0.014 0.004 0.632 0.052
60 0.918 0.255 0.012 0.005 0.598 0.020
0.4 30 0.981 0.772 0.064 0.000 0.719 0.012
40 0.946 2.081 0.089 0.003 0.499 0.035
50 0.962 1.051 0.060 0.008 0.614 0.008
60 0.888 1.506 0.078 0.009 0.408 0.003
0.8 30 0.977 6.113 0.312 0.012 0.535 0.003
40 0.969 5.649 0.322 0.074 0.535 0.004
50 0.977 2.800 0.222 0.053 0.606 0.001
60 0.954 5.650 0.227 0.410 0.453 0.024
1.6 30 0.907 7.570 0.892 0.150 0.236 0.014
40 0.973 2.499 0.825 0.063 0.324 0.012
50 0.956 1.790 0.445 0.082 0.311 0.006
60 0.968 2.013 0.360 0.045 0.347 0.008
3.2 30 0.976 27.91 4.157 0.550 0.297 0.009
40 0.990 9.277 3.037 0.056 0.311 0.030
50 0.990 23.00 2.650 0.035 0.355 0.021
60 0.980 32.06 2.240 0.035 0.348 0.019
NFAIR concentration Temp. (C) R
2

2
(Pas) n
0.2 30 0.973 0.030 0.045 0.003 0.376 0.001
40 0.931 0.012 0.017 0.009 0.365 0.012
50 0.885 0.004 0.016 0.008 0.336 0.012
60 0.961 0.006 0.013 0.011 0.360 0.029
0.4 30 0.988 0.009 0.080 0.002 0.325 0.018
40 0.697 0.055 0.040 0.010 0.172 0.042
50 0.935 0.003 0.012 0.006 0.416 0.012
60 0.997 0.002 0.010 0.009 0.700 0.093
0.8 30 0.956 0.112 0.213 0.012 0.240 0.023
40 0.949 0.042 0.039 0.014 0.382 0.036
50 0.952 0.015 0.020 0.001 0.516 0.002
60 0.974 0.005 0.045 0.002 0.320 0.031
1.6 30 0.974 0.178 0.197 0.050 0.336 0.032
40 0.977 0.332 0.149 0.091 0.428 0.004
50 0.875 0.072 0.150 0.012 0.204 0.002
60 0.963 0.015 0.086 0.020 0.291 0.002
3.2 30 0.967 0.810 2.663 0.071 0.641 0.003
40 0.986 5396 0.924 0.912 0.703 0.002
50 0.997 6560 0.465 0.323 0.696 0.008
60 0.995 166.1 0.136 0.050 0.731 0.004
Temp.: temperature; r: correlation coefcient;
2
: chi-square; : viscosity; n: constant determined from power law type model.
1034 P. Kiran, P.S. Rao / Food Research International 62 (2014) 10291037
and electrostatic bonds formation with existing polymeric cluster net-
work leading to increased viscosity. The recovery of consistency index
was found to be greater in FD and NFAIR at 3.2% (w/v) in comparison
with both FJ and CJ.
3.6. Dynamic oscillation behavior of concentrated dispersions
In dynamic rheological analysis, stress sweep studies were mainly
conducted to nd out the linear viscoelastic region (LVR) and critical
stress point. The critical stress value, where crossover of both storage
(G) and loss (G) moduli takes place, could be dened as the stress
above which structure of the systembroken down. The variation in crit-
ical stress point of preparedA. vera dispersions is presented in Fig. 6. The
critical stress values for FD, HAand DHwere in the range of 82 to 365 Pa
(Table 1). However, FJ and CJ showed lower critical stress values in the
range of 0.040.11 Pa. This discrepancy in critical stress values may be
attributed to the fact, as stated by Lad and Murthy, that the rearrange-
ment of polymeric insoluble ber structures in A. vera juice is very sen-
sitive to applied shear (Lad & Murthy, 2013). But at the same time,
preparation of the brous A. vera powder prepared by different drying
methods causes the structural changes of insoluble bers. The obtained
results further corroborated with SEM micrographs of A. vera powder
(Fig. 3). It implies that, the conformational changes of insoluble bers
are the major one which might be affecting the critical stress point, as
reported in the case of cellulose bers (Rinaudo, Lowys, & Desbrie,
2000). Further, NFAIR showed low critical stress value of 10 Pa and
found to be inversely proportional with a critical volume. It might be
due to the removal of insoluble bers after centrifugation which was
helpful in attaining higher critical volume, followed by extraction of
the soluble polysaccharide, lowering its critical stress. These trends
were in agreement with the swelling effect on hydrogel formation
using A. vera, poly (vinyl alcohol) and poly (N-vinyl pyrrolidone) for
wound treatment as reported earlier (Park & Nho, 2004).
Oscillatory rheology was conducted as a function of frequency which
provides the values of storage modulus (G), loss modulus (G), and
cross over point and it can be utilized as a diagnostic of dispersions ri-
gidity. Experimental data of the above mentioned rheological units at
various frequency ranges such as 9, 1 and 0.1 Hz are shown in Table 3.
Fig. 7Aand Bshowed the variations of viscoelastic modulus as a function
of frequency at 25 C for fresh juices and aqueous brous and non-
brous dispersions at their corresponding critical volume concentra-
tions. In fresh juices, the mechanical response showed the gel nature
where G N G thorough out the frequency sweep (0.110 Hz) with little
frequency dependence, and lower separation between G and G
Fig. 5. Flow curves of prepared dilute A. vera dispersions A) effect of temperature on viscosity of fresh, brous and non-brous samples at 3.2% (w/v) concentration at shear rate 100 s
-1
,
B) effect of concentration on viscosity of brous and non-brous at 30 C at shear rate 100 s
-1
.
Fig. 6. Variation incritical stress points as function of A. vera dispersions measuredat 25 C
at critical volume.
Table 3
Experimentally determined elastic (G) and viscous (G) reported at frequency 9, 1, 0.1 Hz
for fresh juices (FJ and CJ) and prepared aqueous A. vera brous (FD) and non-brous
(NFAIR) dispersions at critical volume (average and standard deviation values of 3 mea-
surements).
Sample
A. vera powder
Frequency G (Pa) G (Pa)
Average Stdev. Average Stdev.
Fibrous juice 9 00025.037 0005.210 0011.619 0002.900
1 00014.265 0001.212 0003.1434 0000.751
0.1 00008.422 0000.910 0002.8344 0000.651
Clear juice 9 00020.257 0004.215 0009.0567 0002.751
1 00004.542 0000.684 0001.7996 0000.754
0.1 00002.767 0000.325 0001.055 0000.650
FD 9 28,806.670 2815.250 6548.001 1316.670
1 22,556.670 1735.291 5231.667 0462.699
0.1 16,550.000 685.492 4789.333 1094.469
DH 9 32,043.330 1970.034 7935.000 1358.340
1 24,533.300 1044.090 5430.330 0884.811
0.1 20,166.700 1024.030 3155.670 0385.665
HA 9 18,923.330 0863.790 4367.660 0382.791
1 15,410.000 0676.165 3133.333 0169.795
0.1 12,320.000 0383.532 2817.333 0123.520
NFAIR 9 00082.200 0008.843 0009.447 0013.274
1 3.04933 0.50026 0002.589 0000.3640
0.1 0.08414 0.03017 0000.447 0000.123
1035 P. Kiran, P.S. Rao / Food Research International 62 (2014) 10291037
(Fig. 7B). This might be due to cell wall polysaccharide interacts with
adjacent polymeric chains present in the surrounding liquid (Lad &
Murthy, 2013). Interestingly, in prepared aqueous brous dispersions,
the mechanical responses were approximately 7001200 times higher
than fresh juices (Table 3). Hence, they predominantly behave as solid
where G N G over the most of accessible frequency range (0.1
10 Hz) with little frequency dependence in either moduli, and they
also showed the higher separation between G and G. DH dispersion
exhibited higher magnitude of elastic modulus than other samples
(Fig. 7A). Increase in elastic modulus of brous dispersions than fresh
juices might be due to the presence of cell wall bre (cellulose) that re-
mains unaffectedunlike cell wall polysaccharides containing pectic sub-
stances already degraded during drying (Femenia et al., 2003).
Furthermore, the dilution with water at critical volume results in acces-
sibility of carboxylate groups, whichmight facilitate the ordering of ran-
dombrous cellulose clusters and thus leading to solid like response.
Frequency sweep of NFAIR uid showed crossover point at 0.83 Hz
indicating viscoelastic behavior. It typically behaves as a gel with G N
G at (N0.80 Hz) higher frequency, and as a liquid with G N G at
(b1 Hz) lower frequency (in Table 3) depicting a solgel behavior and
relatively frequency-dependent moduli. Interestingly, these gels posses
lower magnitude of elastic modulus than A. vera fresh juices and brous
dispersions, but they are showing higher frequency dependence where
two step increase in elastic modulus is seen. This might be due to the
network formation by hydrophobic and hydrogen bond between
water and acetylated polysaccharides portion, responsible for increase
in critical volume, which was more pronounced due to the removal of
brous cell wall portion. The obtained rheological behavior was in ac-
cordance with the previous ndings, where the crossover points were
determined for puried A. vera pectin and partially acetylated
glucomannans (Campestrini et al., 2013; McConaughy, Kirkland et al.,
2008; McConaughy, Stroud, et al., 2008). Furthermore, the dilution
with water results in a high accessibility of bioactive acetyl along with
carboxyl groups, which might facilitate the formations of three dimen-
sional networks of polysaccharide and thus leading to a response like
gel (Campestrini et al., 2013).
4. Conclusions
Presence of the bio-active acetylated functional groups was detected
in all samples, except in hot air dried powder. Prepared aqueous disper-
sions showed shear thinning behavior at all temperatures and concen-
trations examined and it was well described by power law model. The
ow behavior indices for all the dispersions varied from 0.172 to 0.731
whereas the consistency index values were within the range of 0.012
to 4.157 Pas. Decrease in critical volume was detected in brous dis-
persions. The mechanical strength of brous dispersions at their critical
volume values was approximately 1000 times higher than fresh juices
which indicated their solid like behavior (G N G) within the domain
of frequency tested. In contrast, the obtained critical volume for
NFAIR, which showed frequency dependent solgel behavior, was
higher (10 mL H
2
O/100 mg of dry matter). The rheological and structur-
al understanding in prepared Aloe dispersions will be useful to develop
food products with desired functionalities and enhanced stability. How-
ever, applicability of the theoretical models is still a major challenging
area due to their heterogeneity in composition. This opens the door
for investigating the chemical composition of brous powders in detail
and their advancement in preparation of aqueous dispersions.
Abbreviations

0
initial stress

0
initial strain
G elastic modulus
G viscous modulus
G

complex modulus

complex viscosity
dynamic viscosity
angular frequency
phase angle
TTM test tube tilting method
LVR linear viscoelastic region
FJ fresh brous juice
CJ fresh clear juice
FD freeze drying
DH dehumidied air drying
HA hot air drying
AIR alcohol insoluble residue
NFAIR non-brous alcohol insoluble residue
Acknowledgements
This research was partly supported by National Agricultural Innova-
tion Project (NAIP), Indian Council of Agricultural Research (ICAR), New
Delhi, India. The authors thank Dr. P.P. Srivastav, Agricultural and Food
Engineering Department, and Dr. V.V. Rao, Cryogenic Engineering
Fig. 7. Viscoelastic behavior of prepared A. vera dispersions measured at 25 C at critical volume of A) brous dispersions, B) fresh juices and non-brous dispersions.
1036 P. Kiran, P.S. Rao / Food Research International 62 (2014) 10291037
Centre, IIT Kharagpur, India for providing some of the facilities for the
research. The authors acknowledge Dr. J.K. Dey, Department of Chemis-
try for his suggestions and guidance at various stages of research. The
authors also wish to thank Mr. Anirban and Mr. Snehasis Chakraborty,
Research Scholars, Agricultural and Food Engineering Department, IIT
Kharagpur, India, for their needful help during article preparation.
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