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Carbohydrate Polymers
journal homepage: www.elsevier.com/locate/carbpol
a r t i c l e
i n f o
Article history:
Received 20 November 2015
Received in revised form 9 May 2016
Accepted 12 May 2016
Available online 16 May 2016
Keywords:
Resistant cornstarch
Rheology
DSC
Locust bean gum
CLSM
High pressure
a b s t r a c t
In this study, effects of a 30 min high pressure (HP) treatment (200600 MPa) at room temperature on the
rheological, thermal and morphological properties of resistant corn starch (RS) (5% w/w) and locust bean
gum (LBG) (0.25, 0.50 and 1.0% w/v) dispersions were evaluated. Results showed that the storage modulus
(G ), loss modulus (G ), and apparent viscosity values of starch/gum (RS/LBG) mixtures were enhanced
with an increase pressure level, and demonstrated a bi-phasic behavior. HP treated RS/LBG samples were
predominantly either solid like (G > G ) or viscous (G > G ), depending on the pressure level and LBG
concentrations. Differential scanning calorimetry (DSC) analysis of the pressurized mixtures showed a
major effect on gelatinization temperatures (To , Tp ,), and it was observed that RS/LBG mixtures gelatinized completely at 400 MPa with a 30 min holding time. Confocal laser scanning microscopy (CLSM)
images conrmed that at 600 MPa, RS/LBG mixtures retained granular structures and their complete
disintegration was not observed even at the endpoint of the gelatinization.
2016 Elsevier Ltd. All rights reserved.
1. Introduction
Starch/hydrocolloid mixtures are frequently used in the food
industry as they impart better quality and stability to the nal
products. Starches, in their native form, often do not exhibit properties prerequisite for a specic application. (Zhu, 2015). Native
starches are often chemically modied and/or blended with other
components such as hydrocolloids (e.g. guar gum, corn ber gum,
hydroxypropylmethylcellulose (HPMC), xanthan gum) to impart
desirable and amending properties for improving product texture
and rheology (Qiu et al., 2015; Rosell, Yokoyama, & Shoemaker,
2011), enhancing cold-storage and freeze-thaw stability (BeMiller,
2011), moisture retention (Kohajdov & Karovicov, 2009), syneresis (Yamazaki et al., 2013), and resistance to various physical
changes during processing (heat, shear, and acidic medium), retrogradation and breakdown.
Locust bean gum (LBG), also known as Carob gum is a natural
hydrocolloid, which has been used in numerous industrial applications (food, cosmetic, textile, pharmaceutical, paint, milling and
construction industries) because of its ability to produce highly viscous solutions at relatively low concentrations (0.02%) to stabilize
Corresponding author.
E-mail address: hosahalli.ramaswamy@mcgill.ca (H.S. Ramaswamy).
http://dx.doi.org/10.1016/j.carbpol.2016.05.039
0144-8617/ 2016 Elsevier Ltd. All rights reserved.
300
high cholesterol and other chronic diseases (Choi, Lee, Cho, Choi, &
Moon, 2010).
Several studies have reported that the inuence of hydrocolloids
on corn starch is dependent on the structure and concentration
of the hydrocolloid (Funami et al., 2008; Qiu et al., 2015). The
interaction between starch and hydrocolloid is also reported to
be dependent on the starch source, differences in granule size
(Amini et al., 2015) and crystalline microstructure (Techawipharat,
Suphantharika, & BeMiller, 2008). In order to take advantage of
starch/gum interactions and enhance their applications in food
formulations, it is important to assess the inuence of different
physical and chemical processes, such as heat, high pressure (HP)
and/or enzymatic treatments, on their functional and physicochemical properties (Li, Bai, Mousaa, Zhang, & Shen, 2012). The
majority of earlier reports are focused mainly on the nutritional,
functional and digestibility characteristics of resistant starches,
while the use of resistant starches in food formulations often
involve noticeable presence of other hydrocolloids (gums). Therefore, understanding the interactions between RS and gums are of
considerable interest.
High pressure-processing (HPP) is a non-thermal processing
technology used in the food industry for preparing products
with high functional (Ramaswamy, Singh, & Sharma, 2015), nutritional (Ramaswamy, Chen, & Rattan, 2015) and textural (Alvarez,
Ramaswamy, & Ismail, 2008) qualities. Over the last two decades,
the inuence of HP treatment (i.e. pressure level, treatment time,
starch source, concentration, temperature, etc.) on starch gelatinization in general (Ahmed, Ramaswamy, Ayad, Alli, & Alvarez,
2007; Ahmed, Varshney, & Ramaswamy, 2009; Liu, Selomulyo, &
Zhou, 2008; Oh, Hemar, Anema, Wong, & Neil Pinder, 2008; Oh,
Pinder, Hemar, Anema, & Wong, 2008; Stolt, Oinonen, & Autio,
2000) or more specically on gelatinization of corn starch (Ahmed,
Singh, Ramaswamy, Pandey, & Raghavan, 2014; Baszczak et al.,
2007; Buckow, Heinz, & Knorr, 2007) has been widely investigated. The above studies have been focused on understanding the
mechanism of pressure-induced gelatinization and its inuence on
physicochemical and structural properties of starches. HP treatment has been shown to inuence mostly the non-covalent bonds
in starches, so this treatment can cause major structural, textural,
sensory and nutritional damages (Balny, 2002).
In a recent review covering over fty studies (BeMiller, 2011), a
few have focused on the effect of LBG on different starches but none
have included HPP. To the best of our knowledge, there has been no
study on the effect of HP treatment on starch/LBG mixtures to date.
With this background, the aim of this experimental study was to
evaluate the effect of HP treatment on the rheological, calorimetric
(gelatinization) and morphological properties of starch-LBG mixtures. From an industrial point of view, this research is signicant
because of the dearth of basic data on the dynamics of interactions
between LBG and RS treated with HP which will be useful in the
development of RS-gum based food products.
301
Table 1
Storage modulus (G ), loss modulus (G ) at lower (10 rad/s) and higher (50 rad/s) frequencies and apparent viscosity (at 10 s1 ), consistency index (Pa sn ), ow behavior index
for starch (RS), and RS-LBG dispersions with different concentration at 25 C (without and with high pressure processing).
Samples
G at 10 rad/s
G at 10 rad/s
G at 50 rad/s
G at 50 rad/s
(Pa s) at 10 s1
K (Pa sn )
n ()
R2
5% RS
5% RS/0.25% LBG
5% RS/0.50% LBG
5% RS/1.0% LBG
200 HP/5% RS
400 HP/5% RS
600 HP/5% RS
200/5% RS/0.25% LBG
400/5% RS/0.25% LBG
600/5% RS/0.25% LBG
200/5% RS/0.5% LBG
400/5% RS/0.5% LBG
600/5% RS/0.5% LBG
200/5% RS/1.0% LBG
400/5% RS/1.0% LBG
600/5% RS/1.0% LBG
0.03
0.04
2.81
4.40
0.03
0.04
0.03
0.05
0.04
0.04
0.14
0.17
0.16
6.20
17.65
23.12
0.04
0.09
5.36
6.75
0.07
0.08
0.06
0.08
0.08
0.08
0.52
0.57
0.61
8.34
15.35
19.18
0.92
1.16
11.1
15.7
1.62
1.70
1.56
0.68
1.15
1.12
1.60
1.84
1.74
19.1
35.7
48.47
0.37
0.61
15.12
18.35
0.62
0.74
0.60
0.59
0.74
0.73
2.55
2.71
2.78
20.3
26.9
34.64
0.005
0.020
0.060
0.080
0.012
0.010
0.012
0.014
0.017
0.014
0.053
0.051
0.064
0.530
0.740
0.880
4.12
27.1
21.5
25.3
7.23
8.35
7.02
33.7
35.2
38.5
36.2
42.4
44.3
45.8
54.6
58.3
0.72
0.68
0.66
0.66
0.60
0.58
0.57
0.65
0.62
0.59
0.57
0.56
0.54
0.52
0.50
0.50
0.99
0.95
0.98
0.99
0.96
0.98
0.99
0.93
0.96
0.99
0.98
0.99
0.98
0.98
0.99
0.97
Values are average of three determinations (n = 3); k = consistency index (Pa sn ), n = ow behavior index (dimensionless). R2 values are for n and k.
where
is the consistency coefcient and n is the ow behavior index (for
Newtonian uids, n is equal to 1 while it is lower than 1 for pseudoplastic uids).
2.5. Differential scanning calorimetry (DSC)
The gelatinization behavior of starch alone and starch/LBG dispersions (before and after HP treatments) were evaluated using a
differential scanning calorimeter (DSC) (TA Q 2000, TA Instruments,
New Castle, DE, USA). Prior to sample measurements, the DSC
was calibrated using indium standard. The samples (68 mg) were
heated from 20 to 150 C at 10 C/min heating rate. An empty pan
was used as a reference and dry nitrogen at a ow rate of 50 mL/min,
was used as the purge gas. Thermal transitions of treated samples
were used to gather information of the gelatinization behavior of
test samples. After treatment at higher pressure levels (400 MPa),
the RS/LBG dispersions were fully gelatinized, so demonstrated
no gelatinization peaks. Gelatinization peaks in the nominal gelatinization temperature range (7090 C) were also not observed for
some starch/LBG samples.
2.6. Confocal laser scanning microscopy (CLSM)
Morphological characteristics of starch/LBG dispersions were
observed using confocal scanning microscope (Nikon Instruments,
Nikon Eclipse TE 800-E, Radiance 2100, BIO-RAD, Japan). A few
drops of the starch dispersions with or without LBG were transferred to a 2-cavity slide (Electron Microscopy Sciences, Hateld,
PA, USA), sealed with nail enamel and observed within 15 min.
A laser with an excitation wavelength of 488 nm and a 40 airimmersion objective was used. Only transmission detectors were
used. Digital image les were acquired at 1024 1024-pixel resolution using 1 3 zoom factors. At least 4 images were obtained
per sample for each replicate, and representative micrographs were
selected.
2.7. Statistical analysis
All experiments were carried out in triplicate and the results
were reported as mean. Data were analyzed by Minitab 16 anal-
302
Fig. 1. Rheological properties: dynamic mechanical spectra (closed symbols, storage modulus, G ; open symbols, loss modulus, G ) measured at 0.00110% strain of 5% RS
(w/w) alone and in the presence of LBG (0.25, 0.50 and 1% LBG) (RS and LBG stands for resistant corn starch and locust bean gum respectively). All measurements were made
at 25 C.
303
Fig. 2. Rheological properties: dynamic mechanical spectra (closed symbols, storage modulus, G ; open symbols, loss modulus, G ) measured at 0.00110% strain of HP
treated RS LBG (5% w/w) dispersions in the presence of LBG (0.25, 0.50 and 1% LBG) (RS and LBG stands for resistant corn starch and locust bean gum respectively). All
measurements were made at 25 C.
Table 2
DSC measurements for gelatinization properties of resistant corn starch only (RS)
and RS LBG mixtures (with and without high pressure processing).
Samples
5% RS
5% RS/0.25% LBG
5% RS/0.50% LBG
5% RS/1% LBG
200 HP/5% RS
400 HP/5% RS
600 HP/5% RS
200 HP (5%RS/0.25% LBG)
400 HP (5%RS/0.25% LBG)
600 HP (5%RS/0.25% LBG)
200 HP (5%RS/0.50% LBG)
400 HP (5%RS/0.50% LBG)
600 HP (5%RS/0.50% LBG)
200 HP (5%RS/1% LBG)
400 HP (5%RS/1% LBG)
600 HP (5%RS/1% LBG)
Gelatinization Activity
To ( C)
Tp ( C)
56
70
80
80
37
34
32
63
ND
ND
80
ND
ND
80
ND
ND
81
91
85
85
85
74
68
83
ND
ND
85
ND
ND
85
ND
ND
*
Values are average of three determinations (n = 3); ND: Not detected, RS-LBG
(Resistant starch-locust bean gum dispersions), To (onset temperature), Tp (peak
gelatinization).
304
Fig. 3. Effect of HP treatment on the apparent viscosities of HP treated RS LBG (5% w/w) dispersions in the presence of LBG (0.25, 0.50 and 1% LBG) at 25 C (RS and LBG
stands for resistant corn starch and locust bean gum respectively).
305
Fig. 4. CLSM images of 5% resistant corn starch (w/w) containing 0 (A), 0.25% (B), 0.50% (C), (D) 1% LBG (w/v) with HP treatment at 200 MPa (BD 200 A), 400 MPa (BD 400 A)
and 600 MPa (BD 600 A).
306
307
Stute, R., Klingler, R., Boguslawski, S., Eshtiaghi, M., & Knorr, D. (1996). Effects of
high pressures treatment on starches. Starch-Strke, 48, 399408.
Techawipharat, J., Suphantharika, M., & BeMiller, J. N. (2008). Effects of cellulose
derivatives and carrageenans on the pasting paste, and gel properties of rice
starches. Carbohydrate Polymers, 73, 417426.
Vallons, K. J., & Arendt, E. K. (2009). Effects of high pressure and temperature on
the structural and rheological properties of sorghum starch. Innovative Food
Science & Emerging Technologies, 10, 449456.
Vamadevan, V., & Bertoft, E. (2015). Structure-function relationships of starch
components. Starch/Staerke, 67, 5568.
Wang, B., Li, D., Wang, L.-j., Chiu, Y. L., Chen, X. D., & Mao, Z.-h. (2008). Effect of
high-pressure homogenization on the structure and thermal properties of
maize starch. Journal of Food Engineering, 87, 436444.
Yamazaki, E., Sago, T., Kasubuchi, Y., Imamura, K., Matsuoka, T., Kurita, O., et al.
(2013). Improvement on the freeze-thaw stability of corn starch gel by the
polysaccharide from leaves of Corchorus olitorius L. Carbohydrate Polymers, 94,
555560.
Yoo, D., Kim, C., & Yoo, B. (2005). Steady and dynamic shear rheology of rice
starch-galactomannan mixtures. Starch, 57, 310318.
Zhu, F. (2015). Composition structure, physicochemical properties, and
modications of cassava starch. Carbohydrate Polymers, 122, 456480.