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Improvement of rheological, thermal and functional properties of tapioca starch by using gum arabic
Accepted Manuscript Improvement of rheological, thermal and functional properties of tapioca starch by using gum arabic Ajaypal Singh, David J. Gevekea, Madhav P. Yadav PII:
S0023-6438(16)30470-4
DOI:
10.1016/j.lwt.2016.07.059
Reference:
YFSTL 5633
To appear in:
LWT - Food Science and Technology
Received Date: 4 February 2016 Revised Date:
23 June 2016
Accepted Date: 25 July 2016
Please cite this article as: Singh, A., Gevekea, D.J., Yadav, M.P., Improvement of rheological, thermal and functional properties of tapioca starch by using gum arabic, LWT - Food Science and Technology (2016), doi: 10.1016/j.lwt.2016.07.059. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
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Improvement of rheological, thermal and functional properties of tapioca starch by using gum arabic
Food Safety and Intervention Technologies Research Unit
Sustainable Biofuels and Co-Products Research Unit
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Ajaypal Singh1*, David J. Geveke1*, Madhav P. Yadav2
Eastern Regional Research Center, Agricultural Research Service,
U.S. Department of Agriculture, 600 East Mermaid Lane,
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Wyndmoor, PA 19038, USA
*Corresponding Authors: A. Singh - Tel: 215-233-6349; e-mail: [email protected];
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D. Geveke - Tel: 215-233-6507; e-mail: [email protected]
Mention of trade names or commercial products in this publication is solely for the purpose of
providing specific information and does not imply recommendation or endorsement by the U.S. Department of Agriculture. USDA is an equal opportunity provider and employer.
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Keywords: Viscoelastic properties, Gum arabic, Tapioca starch, Swelling power, Solubility, Pseudoplasticity.
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Abstract
Gum arabic (GA) is a fairly inexpensive gum and is well known for its stabilizing, emulsifying, and thickening properties. The effects of adding GA (0.1-1.0%) on solubility, pasting, and
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rheological properties of 5% native tapioca starch (TS) were analyzed. Dynamic viscoelasticity measurements showed that the elastic modulus (G’) and the viscous modulus (G”) increased in
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the presence of GA, suggesting a strong interaction between GA-TS in the composite system. GA (0.1-1.0%) when used in the TS-GA composite system , indicated higher elasticity (G’>G”). Pasting properties revealed that the peak viscosity and setback of the TS-GA dispersion decreased with increasing concentration of GA, suggesting the importance of GA in controlling
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overall viscosity. The flow behavior index (n) decreased from 0.99 to 0.23 as the concentration of GA in the dispersion increased, indicating pseudoplastic behavior (n < 1). However, the consistency coefficient increased by 5 time, from 0.006 to 0.283 Pa.s. with increasing GA
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concentration (0.1 - 1.0), showing the synergistic effect of GA. These results show that low
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concentrations of GA can beneficially improve the rheological behavior of TS. In addition, GA has advantages of being low cost, clean label, and fewer calories, thus broadening the application spectra of native starches.
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Introduction Tapioca starch (TS) is typically used as a thickening and gelling agent in many food products.
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TS forms a clear, stringy and cohesive paste with bland flavor and is used in a number of food industry applications (Chaisawang and Suphantharika, 2006; Pongsawatmanit et al., 2007; Chang et al., 2014; ; Kim et al., 2015). In general native starches do not have properties that make them ideally suited for applications in food products. Usually starch is modified by
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dervatization to improve its functionalities before being used in processed food formulations.
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Since food processors would prefer not to use the modified food starch label designation required, when chemically modified starches are used, there is considerable interest in starches with desired functionalities that have not been chemically modified (BeMiller, 2015; Wongsagonsup et al., 2014; Puncha-arnon et al., 2015). It is well known that addition of gums/hydrocolloids also improves the functionality of starch by altering its rheological/structural
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and gelatinization properties (Chaisawang and Suphantharika, 2006; Qiu et al., 2015; Chranioti et al., 2015 ; Lomeli Ramirez et al., 2014). In addition, gums can improve starch’s moisture content, water holding capacity and overall product quality without adding much calorific value
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(Funami et al., 2005; Choi et al., 2006; Arismendi et al., 2013; Nwokocha and Williams., 2014;
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Fadavi et al., 2014 ).
In the baking industry, it is more advantageous to use starch from tapioca than from other sources. Due to its clear paste with a bland taste and relatively high viscosity, TS has widespread usage in the food industry including bread, cakes, extruded cereals, beverages, sauces, and pie fillings in its gelatinized form (Chaisawang and Suphantharika, 2006). Native (unmodified or pure) starches have many undesirable properties such as low water holding capacity, retrogradation and syneresis (Wang et al., 2009; Zhu, 2015). These undesirable properties of
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native starch can be rectified either by modification or by the addition of gums (food hydrocolloids). Generally, Gums have benefits over the modification process because of their non-calorific value (calorie free) as well as better retainment of texture and stability during
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processing (Shi and BeMiller, 2002). These advantages have led to widespread usage of starch and gum combinations in a variety of food products (Kayacier and Dogan, 2006; Barros
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Fernandes et al., 2014; Gul et al., 2014; Ladjevardi et al., 2015).
Starch and gum combinations have been studied by many investigators. Chaisawang and
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Suphantharika (2006) studied the effect of the addition of xanthan gums on swelling, gelatinization and freeze-thaw stability of TS. They found that TS granules were completely wrapped by a tight adhering of xanthan gum, which caused their delayed swelling and retardation of gelatinization. In a very recent study, addition of gum arabic (GA) into a TS suspension showed a reduction in swelling power, solubility index and peak viscosity, which
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states that GA can be used as a stabilizer and viscosity controlling agent in the food industry (Chen et al., 2015). On similar lines, synergistic interactions between starch and gums have been
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studied by many researchers (Feng et al., 2012; Qiu et al., 2015; Chranioti et al., 2015; Chivero et al., 2016; Sanz et al., 2016).
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Although the modification of these food macromolecules by physical (thermal/nonthermal processing) and chemical means can also achieve some of the above mentioned objectives, these methods are not cost effective (Lee et al., 2005; Singh et al., Hong et al., 2016; Singh et al., 2014; Flores et al., 2010; Ahmed et al., 2014; Wongsagonsup et al., 2014; Singh et al., 2015, Ramaswamy et al., 2015) and the chemical modification is not considered natural. Therefore, it
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is of considerable practical importance to understand the role of gum interactions on the rheological properties of starch pastes.
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GA is commonly used as a stabilizer in the food industry. It is a weak polyelectrolyte that carries carboxyl groups and can be used as a source of dietary fiber (Nasir et al., 2008; Chen et al., 2015). The addition of GA to potato starch has been shown to lower the peak viscosity (Lee
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et al., 2002). In a similar study by Chen et al. (2015), GA was found to lower the peak viscosity and swelling power leading to a delay of retrogradation. These aspects can be attributed to many
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factors including molecular structure, interaction of amylose and amylopectin and ionic charges of starch and hydrocolloids (Sudhakar et al., 1996; Sanchez et al., 2002; Chaisawang and Suphantharika, 2006; Yadav et al., 2007; Ma et al., 2015)
Despite several studies done on the effect of gum on the starch properties, the effect of GA on
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the rheological, swelling and pasting behavior of native TS has not been investigated. Thus, the aim of the present study was to investigate the beneficial effect of GA on the swelling power (SP), solubility index (SOL), pasting, viscoelastic characteristics and flow behavior of native
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tapioca starch.
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2. Materials and Method
2.1. Materials
A native tapioca starch (TS) was bought from a local store with average particle size 10–15 µm; moisture content 12.8 ± 0.2%; ash content <0.5%; fat content <0.15%; and protein content 0.5%.. The starch was used as received, and their proximate composition (dry weight basis) mentioned above was provided by the manufacturer. Starch samples were verified for moisture
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content by a hot air oven drying method at 130°C until a constant weight was obtained in triplicates. The observed moisture content data varied from the supplier data by less than 1%.
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Gum arabic (GA) was purchased from Fischer Scientific
2.2 Viscoelastic dynamic rheometry:
The dynamic viscoelastic properties of TS and TS-GA mixtures were measured in triplicate
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using a controlled stress rheometer (AR 2000, TA Instruments, New Castle, DE, USA). A parallel-plate 60 mm geometry with a gap of 1 mm was used. To obtain a linear range for the
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dynamic analysis, the linear region was found at a strain of 2%, and a strain of 0.5 % was used to keep the tests in that region. A solvent trap with mineral oil was used to minimize water loss during the measurement. Frequency sweep tests (0.01–10 Hz) were carried out in the linear regime, at constant strain (0.5%) at 25◦C. All the rheological measurements were performed in
Rheology software.
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triplicate, and rheological parameters (G′, G″) were obtained directly from the TA Advantage
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2.3 Steady state characterization:
The steady flow measurements were performed on the same sample to obtain shear rate versus
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shear stress (flow curves) data. The 2 degree 60mm plate was programmed to ramp the shear rate from 0.1 to 100 s−1 in duplicates. Data from the samples was used to estimate the fit of this data to the power law using the following equation: σ = Kγn
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where σ is the shear stress (Pa), γ˙ is the shear rate (s−1), K is the consistency coefficient (Pa sn), and n is the flow behavior index (dimensionless).
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2.4 Pasting properties:
Pasting properties of TS and TS-GA mixtures were determined by a starch pasting cell attachment on the TA rheometer (AR 2000, TA Instruments, New Castle, DE, USA). The
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mixtures were made by first dispersing GA in water at concentrations of 0.1. 0.3, 0.6 and 1.0% (w/w) with magnetic stirring, and then starch (5%) was added to the gum solutions. The TS was
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added slowly to the mixtures with stirring to avoid any lump formation. These TS-GA mixtures were poured into the starch pasting cell for measurement of pasting properties. The samples were first stirred (100 s-1) for 10 s at 30°C, and then the shear rate was held at 30 s-1 until the end of the test. The sample was heated from 30°C to 95°C at 15°C /min and the temperature was held
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at 90°C for 5 min. Afterward, the sample was cooled to 30°C at 15°C/min and held at 30°C for 5 min. TA Instruments rheology data analysis software was used for calculating the following parameters: pasting temperature (PT): the temperature at which viscosity starts to rise; peak
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viscosity (PV); the highest viscosity recorded throughout heating; hot paste viscosity (HPV): the viscosity value at the end of the isothermal period at 90°C; and cold paste viscosity (CPV): the
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viscosity value at the end of the isothermal period at 30°C (Martínez-Cervera et al., 2014).
2.5. Swelling power and solubility index:
Swelling power (SP) and solubility index (SOL) were determined using the method of Leach, McCowen, and Schoch (1959) with some modification. Starch dispersions were centrifuged and heated in a water bath at temperatures of 90°C for 5 minutes. The average heating rate as
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recorded by thermocouples placed in tubes was 18°C/min. Constant stirring was applied in order to prevent any sedimentation. After heating, samples were centrifuged (3000 rpm, 15 min). The precipitated paste was separated from the supernatant and weighed (Wp). Both phases were dried
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at 105°C for 24 h and the weight of dry solids in precipitated paste (Wps) and supernatant (Ws) were calculated. SP is the ratio of the weight of swollen starch granules after centrifugation (g) to
(hydrated starch granules (g) /dry granules in precipitated paste (g))
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SP =
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their dry mass (g).
(1)
The SOL is the percentage of dry mass of solubles in the supernatant (Ws) to the dry mass of whole starch sample (W0).
100% (soluble solids (g) / whole starch sample (g))
2.6 Statistical analyses:
(2)
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SOL =
The experiment consisted of two full treatment replications, while individual replicate analyses
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of the film were conducted at least in duplicate. Statistical analyses were carried out by the
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analysis of variance (ANOVA) using SAS 9.2 software (SAS Institute, Cary, NC, USA). Duncan's multiple range test (p < 0.05) was used to determine the statistical differences among the mean values.
3. Results and Discussion
3.1 Pasting properties:
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This study was the first of its kind to evaluate the impact of gum arabic (GA) with increasing concentration on pasting properties of tapioca starch (TS) system. Different parameters were measured to compare the peak viscosity (PV), hot paste viscosity (HPV), cold paste viscosity
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(CPV), relative breakdown (RB) and total setback (TSB). It has been observed by many investigators that addition of hydrocolloids alters the pasting properties of starch. This study has very clearly demonstrated that addition of GA results in a significant (P<0.05) decrease in PV,
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RB, and TSB values (Table 1). The GA presumably covered most of the TS granules and promoted granules association, which restricted swelling of the granules and limited the increase
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in viscosity during pasting. The addition of GA into TS had an antagonistic effect as it caused a decrease in PV of the biphasic TS-GA system. A similar trend was reported, which showed a reduction of PV, RB, and TSB viscosities upon addition of xanthan gum into tapioca starch (Chaisawang and Suphantharika, 2006). One of the possible reasons for delay in pasting and
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reduction in PV was retardation of granule destruction and leaching of amylose, when negatively charged starch solution were heated with anionic gums, as explained in detail by Shi and BeMiller (2002). They also explained that such effects were due to interactions between leached
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amylose molecules and gums used.
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The GA utilized in this experiment had a low molar mass (1.86 × 105 g mol−1), which was comparatively lower than some other polysaccharides (Renard et al., 2012.) It was found that most of the hydrocolloids increase the viscosity but the hydrocolloids with lower molecular mass may lead to a decrease in the viscosity as described in the case of corn fiber gum and guar gum (Qiu et al., 2015b; Funami et al., 2005b), which may be useful in terms of controlling viscosity of emulsion/mixture/dispersions. In a similar study, it was found that the main reason for the decreased viscosity was the lower molar mass of guar gum (4.7 x 105 g mol−1) as described by
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Funami et al. (2005b). They explained that the lower molecular mass of guar gum produced a smooth flow and prevented the abrasion of starch granules without interacting with amylose or
start to rupture and breakdown leading to a PV decrease.
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amylopectin leaching. When a starch suspension reaches its maximum viscosity, its granules
Heating of a TS-GA system leads to gelatinization of the starch granules, which in turn increases
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the viscosity of the overall system. The main reason for such behavior is that the gum arabic (GA) is located in the continuous phase and its concentration is increased as the volume of the
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starch phase accessible to GA is reduced due to swelling during gelatinization (Alloncle et al., 1989). This increase in viscosity is mainly due to swollen granules and when shear forces are exerted, it results in the loss of granule integrity and further disruption leading to an increase in the paste viscosity. This later phenomenon is defined as breakdown viscosity and is clearly seen in the TS-GA interactions in the present study, which agrees with other investigator’s findings
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for starch and gum mixtures (Christianson et al., 1981; Ahmed et al., 2014; Qiu et al., 2015a).
The change in the PV during heating (Table 1) clearly indicated that there was starch
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gelatinization upon heating. It was also visible that there was a strong impact of the addition of GA to the TS dispersion. The peak viscosity decreased from 0.052 to 0.038 Pa.s after the
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addition of 1.0% GA. There was a gradual decline in the PV with increasing concentration of GA from 0.1 to 1.0%.
Relative breakdown (RB) was used instead of traditional breakdown to quantify the degree of the starch structure change. There was a gradual increase (-0.2456 to -0.1316) in the RB values by increasing the concentration of GA (0.0 to 1.0%) in the TS-GA mixture. Relative breakdown (RB) gives the degree of starch structure breakdown during cooking and has the advantage of
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eliminating the differences attributed to different initial PV values, allowing correct comparison among different samples. The total setback (TSB) is the final increase in the viscosity during the cooling phase which is related to the retrogradation phenomenon. The effect on TSB was
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markedly visible (decreasing from 0.037 to 0.017) with increasing concentration of GA from 0.11.0%. TSB values of TS-GA dispersions decreased by a factor of more than ½ with increasing concentration of GA from 0.1 to 1.0%. The TS-GA interaction can be influenced by a number of
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factors including amylose content, length of amylose molecules and the state of dispersion of the
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amylose chains (Chaisawang and Suphantharika, 2005; Singh et al., 2010).
3.2 Flow behavior
The dispersion of TS-GA mixtures was evaluated at 25◦C for determining their rheological behavior. The shear stress- shear rate graphs show that increasing concentration of gum arabic in
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the TS-GA mixtures from 0.1 to 1.0% lead to an increase in the flow behavior (Figure 1). When the shear rate and the shear stress data were fitted to various models, these TS-GA mixtures data fitted well to the power law with high regression coefficient (R2 ≥0.93) (Table 2). Newtonian
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fluids have flow behavior of 1 and values lesser than 1 are considered non-newtonian (pseudoplastic behavior) (Lu et al., 2012; Ahmed et al., 2014). In the present study, (control) TS
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and all TS-GA mixtures were found to show pseudoplastic behavior. The flow behavior index (n value) of TS-GA mixture was found to consistently decrease from 0.47 to 0.23 with increasing concentration of GA from 0.1-1.0%. The control TS sample was a mixture of starch and water which exhibited shear thinning behavior very similar to that of the TS-GA mixtures (Table 2). An increase in the pseudoplasticity might be due to the higher degree of structural breakdown during shearing at higher GA concentration in the TS-GA mixture. A similar trend was also
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found by Chen et al., 2015, where the addition of Gum arabic to the Tapioca starch led to the lower value of the n index.
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The consistency coefficient (k) acts as an indicator of viscosity and was determined from the flow data. The mixture of TS-GA with the highest concentration of GA (1.0 %) showed a k value of 0.283, which was almost 50 times greater than TS control (k value =0.006). The consistency
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coefficient (k) showed a consistent increase following the increasing trend of GA percent concentration (i.e. 1.0>0.6>0.3>0.1>control). It has been found that an increase in the
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concentration of GA causes an increase in intermolecular interactions or entanglement which leads to increase in consistency coefficient (Chen and Chen, 2001). Flow index (n) and consistency coefficient (k) show that the changes in the flow properties of TS-GA mixtures are highly dependent on the GA concentration.
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Although the concentrations of GA in the TS-GA mixture were low, the apparent viscosity (η10) of the mixture was highly affected (0.005 to 0.048 Pa-s) with increasing concentration (0.1 to 1.0 %) of GA (Table 3). All the samples including control showed non-Newtonian behavior as the
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η10 decreased with increasing shear rate (Figure 2). The η10 value of the control sample (0.005) increased three times to 0.018 by addition of just 0.1% GA. These results demonstrate for the
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first time, that addition of a small amount of GA (even 0.1%) caused a major change in the η10 apparent viscosity of the TS-GA mixture.
Similar trends were observed for the tapioca starch- gum arabic (Chen et al., 2015) and corn fiber gum-maize starch (Qiu et al., 2015a). The increase in the η10 of TS-GA suspensions might be due to a synergistic effect of GA. Similar increases in the viscosity of many cationic, anionic and neutral polysaccharides by interaction with corn fiber gum (CFG) have been reported (Zhang et
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al. 2015) and it has been interpreted that it was due to the synergistic effect of CFG on the polysaccharides studied. The increase in η10 has also been reported for other gum and starch
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systems and was thought to be due to their physical interactions (Warrand et al., 2005).
3.3 Viscoelastic characterization
Viscoelastic properties are used for the viscous and elastic characterization of food samples
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(Kealy, 2006; Ahmed et al., 2015). The control TS and TS-GA dispersions were studied in terms of rheological changes by employing the frequency range of 1-10 Hz. There was an increasing
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trend in the viscoelastic properties (G”, G’ & tan δ) with increasing frequency from 0.1-10 Hz (Figures 3, 4 and Table 3). The rheological properties analysis showed a greater structural rigidity as indicated by the increase in G′ and G″ values with increasing concentration of GA in the mixtures (Table 3). There was a significant frequency dependency of the dynamic moduli for
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all TS-GA mixtures. This suggests that there was a strong interaction between GA and TS amylose in the composite system. The higher the frequency, the more was the mixture elasticity (G′>G″) in the studied frequency interval. Viscoelastic characterization indicates that addition of
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GA leads to a predominantly elastic behavior (Table 3). These results clearly indicate that the
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GA-TS mixtures are in the weak gel category (Clark and Rosse Murphy, 1987; Qiu et al., 2015)
The control sample containing 5% TS showed a very similar behavior like TS-GA mixtures in terms of viscous and elastic behavior with increasing frequency, but the elastic modulus G’ was predominant over the viscous modulus G" at both low and high frequencies (Table 3). With the addition of GA to TS and its increasing concentration from 0.1 to 1.0%, there was a corresponding increase in both the viscous and the elastic moduli (G’ and G”). However, when the concentration of GA in the TS-GA mixture was near the lower end (0.1-0.3%), the amount of
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increase in the G’ and G” values was small. But when the concentration of GA in the TS-GA mixture was near the higher end (0.6-1.0%), there was a significant increase (about 3 to 4 times) in the G’ and G” values (Table 3). These results clearly indicate that the extent of viscoelastic
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properties, especially elasticity was higher at the higher concentration of GA used. Similar results were reported on a maize starch – flaxseed gum mixture study, where the G’ value was nearly an order of magnitude higher than the G” value in the experimental range for all samples
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(Mohammed et al., 1998). The tan δ is an indicator of viscoelastic properties and is the ratio of G’ and G”. The tan δ values were changed by addition of GA . At lower concentrations of GA in
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the TS-GA mixtures (0.1-0.3%), tan δ gradually increased by 70% showing a more liquid-like behavior. However, at higher GA concentrations (0.6-1.0%), there was a decreasing pattern of tan δ values showing that the TS-GA mixtures had a more solid-like behavior than the control TS. There is a possibility of a threshold level after 0.3% concentration as the tan δ plummeted
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above this concentration.
3.4 Swelling power and solubility index:
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The gelatinization process leads to the swelling of the starch granules, which then ruptures and amylose leaches out of the granules. The amount of swelling of starch granules by the
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gelatinization process is dependent on its amylopectin content, but its amylose acts as a swelling inhibitor (Chaisawang and Suphantharika, 2005; Hong et al., 2016).
Swelling power (SP) and solubility index (SOL) were determined following the method of Mandala and Bayas, 2004. It has been generally observed that upon heating of starch suspensions, the starch granules imbibe quickly and rupture due to disruption of amylopectin double helices (Biliaderis, 2009). Swelling is considered as a two stage process: an initial slow
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process followed by a faster one afterward (Kokkini et al., 1992; Mandala and Bayas, 2005). Swelling power of tapioca starch (TS) was found to have a SP value of 1.29. Upon addition of GA and increasing its concentration, there was no systematic effect observed for the SP. There
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were changes with the addition of GA, but the changes were insignificant (P<0.05). The SP behavior of the TS-GA mixtures followed a trend similar to peak viscosity (PV) shown in Tables 1 & 4. In a similar study, when guar or xanthan gum was added to native tapioca starch, the SP
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of native starch–xanthan gum mixture was almost unchanged (Chaisawang and Suphantharika, 2006). This was due to the restricted swelling of the starch granules caused by the tightly
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wrapped xanthan gum layer. This current study showed similar results to that of above cited study of Chaisawang and Suphantharika, 2006. It is generally known that a small increase in the SP is also marked by a small decrease in peak viscosity (PV) during starch pasting as evidenced in Table 4. Mandala and Bayas, 2004 found a very similar trend in their study when xanthan
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gums were added to starch mixtures. However, different trends were observed for SOL. Control TS had a SOL value of 178.4, which almost doubled to 365 with the addition of only 0.1% GA. By increasing the concentration of GA from 0.1 to 1.0%, a further increase in SOL value from
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365 to 665 was observed. The TS-GA mixture showed the following increasing trend in SOL: TA+GS 1%> TA+GS 0.6%> TA+GS 0.3 %> TA+GS 0.1%> control TS with the addition of
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GA. These differences in swelling power may be attributed to the differences in amylose content, viscosity patterns and weak internal organization resulted from negatively charged groups within the starch granules (Singh et al., 2003). By increasing the concentration of gum arabic in GA-TS mixture, there was an increase in the swelling of granules during heating and many large granules were observed even at relatively low temperature (75 °C). Amylose leakage increases also during heating until 85°C which acted as a restricting temperature. Due to gum arabic
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effects on granules swelling and SOL, it was visible that the viscosity and consistency of GA-TS mixture heated together at 75 °C would be relatively high.
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3.5 Relationship between rheological, thermal and functional properties The effect of gum arabic on the functionality of tapioca starch has been explored by determining the following properties: rheological, thermal and functional properties. A correlation between
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viscoelastic parameters (G′, G′′) and apparent viscosity (ɳ10) was found. The strong increase in elastic and viscous modulus of TS-GA mixture correlates well with apparent viscosity (Table 3).
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Similarly, the solubility show a strong correlation with the consistency coefficient and it was found that both of these characteristics increased many folds with increasing concentrations of gum arabic. Flow behavior showed a decreasing n value which indicates pseudoplastic behavior upon shearing. This pseudoplastic behavior showed a similar trend to that of pasting behavior.
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Pasting values such as peak viscosity and HPV showed a trend similar to that of the flow behavior index, which indicates that upon heating and shearing, the mixture of GA and TS might show a similar effect. Swelling power (SP) and solubility (SOL) can be used to assess the extent
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of interaction between starch chains, within the amorphous and crystalline domains of the starch granule (Ratnayake et al., 2002). The ability of starches to swell in excess water and their
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solubility also differed significantly as solubility and swelling properties showed entirely different trends (Table 4). Due to the capability of adsorbing more water, increasing concentration of gum arabic in the tapioca starch showed increasing tan δ, and exhibited more liquid phase as indicated by high tan δ. Interrelationship between swelling power and peak viscosity during pasting behavior was observed. These results are consistent with previously reported findings on interactions between starch and gums (Chaisawang and Suphantharika, 2005; Chaisawang and Suphantharika, 2006; Chen et al., 2015).
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Conclusion
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Currently, there is trend in market towards clean label food, which implies no chemical modifications. The addition of gum arabic (GA) to native tapioca starch (TS) improved its pasting, rheological properties, and functionalities (swelling power and solubility index). But
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there was no particular trend in the swelling power of TS with the addition of GA. The viscoelastic properties were found to increase with increasing concentration of GA with elastic
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modulus slightly higher than the viscous modulus. The flow behavior index showed pseudoplastic behavior with increasing concentration of GA in the TS-GA mixture. Nevertheless, the consistency coefficient increased almost 5 times from the control sample to the TS-GA sample with 1% GA. A strong relationship was noticed between solubility index and G”
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on the addition of GA to TS composite. Thus, it can be concluded from these results that GA can modify a native starch giving a more solid like rheological behavior by strengthening its network structure. Therefore, clean label gums can be used to improve functioanlity of the starches
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without any chemical modification.
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Acknowledgements
This research was supported in part by an appointment to the ARS Research Participation Program administered by the Oak Ridge Institute for Science and Education (ORISE).
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suspensions during pasting. Carbohydrate Polymers, 50(1), 7-18. 53. Wang, Y., Wang, L. J., Li, D., Özkan, N., Chen, X. D., & Mao, Z. H. (2008). Effect of flaxseed gum addition on rheological properties of native maize starch. Journal of Food
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Engineering, 89(1), 87-92.
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56. Wongsagonsup, R., Deeyai, P., Chaiwat, W., Horrungsiwat, S., Leejariensuk, K., Suphantharika, M., Fuongfuchat, A., & Dangtip, S. (2014). Modification of tapioca starch by non-chemical route using jet atmospheric argon plasma. Carbohydrate polymers, 102,
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790-798.
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properties. Cereal Chemistry, 84(2), 175-180.
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Molecular characteristics of corn fiber gum and their influence on CFG emulsifying
58. Yadav, M. P., Moreau, R. A., Hotchkiss, A. T., & Hicks, K. B. (2012). A new corn fiber polysaccharide
isolation
process
that
preserves
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gum
functional
components.
Carbohydrate Polymers, 87(2), 1169-1175.
59. Zhang, F., Luan, T., Kang, D., Jin, Q., Zhang, H., Yadav, M. P. (2015) Viscofying properties of corn fiber gum with various polysaccharides, Food Hydrocolloids, 43 218F.
(2015).
Composition,
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227.Zhu,
structure,
physicochemical
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modifications of cassava starch. Carbohydrate polymers, 122, 456-480.
properties,
and
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Tables Table 1. Pasting properties of tapioca starch and its mixture with various concentrations of gum
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arabic.
Peak Vis (Pa.s)
HPV*
CPV**
(RB)
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Conc.
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Relative breakdown
Total setback (TSB)
[(PV-HPV)/PV]
CPV- HPV
0.052
0.064
0.11
-0.246
0.037
5%TS+0.1 GA
0.058
0.070
0.11
-0.207
0.040
5%TS+0.3 GA
0.054
0.061
0.09
-0.220
0.029
5%TS+0.6 GA
0.050
0.062
0.09
-0.170
0.028
0.043
0.06
-0.132
0.017
EP 0.038
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5%TS+1.0 GA
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5 % TS
* Hot paste viscosity
** Cold paste viscosity
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Table 2. Flow properties of tapioca starch and its mixture with various concentrations of gum arabic
n
k( Pa.sn)
5% TS
0.990±0.01
0.006±0.001
0.99
5% TS + 0.1% GA
0.470±0.01
0.063±0.001
0.98
5% TS + 0.3% GA
0.330±0.01
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0.129±0.020
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5% TS + 0.6% GA
5% TS + 1.0% GA
0.201±0.010
0.96
0.235±0.01
0.283±0.010
0.95
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0.93
0.296±0.02
K, consistency coefficient (Pa.sn); n, flow behavior index (dimensionless).
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R2
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Mixtures
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G'
G'
10 rad/s 10 rad/s 50 rad/s 50 rad/s
0.110
0.087
5%TS+0.1% GA
0.133
0.119
3.740
5%TS+0.3% GA
0.145
0.216
5%TS+0.6% GA
0.713
0.291
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0.991
1.689
1.364
0.296
ɳ10 (Pa-s)
tan δ
10 s-1
10 s-1
0.005
0.792
1.220
0.018
0.889
2.580
2.544
0.027
1.487
4.543
3.540
0.039
0.408
8.990
3.784
0.048
0.299
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5% TS
5%TS+1.0% GA
G"
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Samples
G"
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Table 3. Apparent viscosity (η10) at 10 s-1 & viscoelastic parameters (G’, G”) at low and high frequencies (10 & 50 rad/s) using different TS-GA concentrations at 25°C.
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Table 4. Swelling power (SP) and solubility index (SOL) as affected by addition of gum arabic
Concentration
swelling power SP
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to tapioca starch.
SOL
1.29 ± 0.05
178.40 ± 1.52
5%TS+0.1% GA
1.24 ± 0.02
365.67 ± 2.25
5%TS+0.3% GA
1.23 ± 0.03
5%TS+0.6% GA
1.30 ± 0.03
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477.42 ± 4.25 584.21 ± 2.58
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5%TS+1.0% GA
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5% TS
665.47 ± 3.58
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Figures
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2.250
2.000
5% TS +0.1% GA 5%TS +0.3% GA 5% TS+0.6% GA 5%TS+1% GA 5% starch only
1.250
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shear stress (Pa)
1.500
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1.750
1.000
0.7500
0.2500
0 10.00
20.00
30.00
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0
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0.5000
40.00 50.00 60.00 shear rate (1/s)
70.00
80.00
90.00
100.0
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Figure 1: Effect of increasing concentration of gum arabic on flow behavior (shear stress/ shear rate curve) in the TS-GA mixture
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Shear rate (1/s) 0
10
20
30
40
50
60
70
80
90
0.5
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0.05
5% TS +1.0% GA
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Apparent Viscosity )Pa.s)
5% Starch
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0.005
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Figure 2: Rheogram representing the change in apparent viscosity of TS-GA mixture as a function of shear rate
100
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10.00
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G' (Pa)
1.000
0.1000
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0.01000
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5% starch, Frequency sweep step 5%TS-1, Frequency sweep step 5%TS-0, Frequency sweep step 5%TS- , Frequency sweep step 5%TS &0, Frequency sweep step
1.000E-3 0.1000
1.000 frequency (Hz)
10.00
Figure 3: Effect of increasing concentration of gum arabic on elastic modulus (G’) in the TS-GA
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mixture
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10.00
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G'' (Pa)
1.000
0.1000
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0.01000
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5% starch, Frequency sweep step 5%TS-1, Frequency sweep step 5%TS-0, Frequency sweep step 5%TS- , Frequency sweep step 5%TS &0, Frequency sweep step
1.000E-3 0.1000
1.000 frequency (Hz)
10.00
Figure 4: Effect of increasing concentration of gum arabic on viscous modulus (G”) in the TS-
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GA mixture
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Highlights
1. Gum Arabic can used to improve functionality of this native starch.
3. Gum arabic improves functionality of native tapioca starch. 4. Gum arabic and tapioca starch gives highly viscous gels.
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2. Gum arabic has an advantage of being clean label, cheaper, less calorific value.
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5. These gels will open up new avenues of gums in the starch application market.
S0023-6438(16)30470-4
DOI:
10.1016/j.lwt.2016.07.059
Reference:
YFSTL 5633
To appear in:
LWT - Food Science and Technology
Received Date: 4 February 2016 Revised Date:
23 June 2016
Accepted Date: 25 July 2016
Please cite this article as: Singh, A., Gevekea, D.J., Yadav, M.P., Improvement of rheological, thermal and functional properties of tapioca starch by using gum arabic, LWT - Food Science and Technology (2016), doi: 10.1016/j.lwt.2016.07.059. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
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Improvement of rheological, thermal and functional properties of tapioca starch by using gum arabic
Food Safety and Intervention Technologies Research Unit
Sustainable Biofuels and Co-Products Research Unit
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2
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1
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Ajaypal Singh1*, David J. Geveke1*, Madhav P. Yadav2
Eastern Regional Research Center, Agricultural Research Service,
U.S. Department of Agriculture, 600 East Mermaid Lane,
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Wyndmoor, PA 19038, USA
*Corresponding Authors: A. Singh - Tel: 215-233-6349; e-mail: [email protected];
†
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D. Geveke - Tel: 215-233-6507; e-mail: [email protected]
Mention of trade names or commercial products in this publication is solely for the purpose of
providing specific information and does not imply recommendation or endorsement by the U.S. Department of Agriculture. USDA is an equal opportunity provider and employer.
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Keywords: Viscoelastic properties, Gum arabic, Tapioca starch, Swelling power, Solubility, Pseudoplasticity.
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Abstract
Gum arabic (GA) is a fairly inexpensive gum and is well known for its stabilizing, emulsifying, and thickening properties. The effects of adding GA (0.1-1.0%) on solubility, pasting, and
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rheological properties of 5% native tapioca starch (TS) were analyzed. Dynamic viscoelasticity measurements showed that the elastic modulus (G’) and the viscous modulus (G”) increased in
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the presence of GA, suggesting a strong interaction between GA-TS in the composite system. GA (0.1-1.0%) when used in the TS-GA composite system , indicated higher elasticity (G’>G”). Pasting properties revealed that the peak viscosity and setback of the TS-GA dispersion decreased with increasing concentration of GA, suggesting the importance of GA in controlling
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overall viscosity. The flow behavior index (n) decreased from 0.99 to 0.23 as the concentration of GA in the dispersion increased, indicating pseudoplastic behavior (n < 1). However, the consistency coefficient increased by 5 time, from 0.006 to 0.283 Pa.s. with increasing GA
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concentration (0.1 - 1.0), showing the synergistic effect of GA. These results show that low
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concentrations of GA can beneficially improve the rheological behavior of TS. In addition, GA has advantages of being low cost, clean label, and fewer calories, thus broadening the application spectra of native starches.
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Introduction Tapioca starch (TS) is typically used as a thickening and gelling agent in many food products.
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TS forms a clear, stringy and cohesive paste with bland flavor and is used in a number of food industry applications (Chaisawang and Suphantharika, 2006; Pongsawatmanit et al., 2007; Chang et al., 2014; ; Kim et al., 2015). In general native starches do not have properties that make them ideally suited for applications in food products. Usually starch is modified by
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dervatization to improve its functionalities before being used in processed food formulations.
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Since food processors would prefer not to use the modified food starch label designation required, when chemically modified starches are used, there is considerable interest in starches with desired functionalities that have not been chemically modified (BeMiller, 2015; Wongsagonsup et al., 2014; Puncha-arnon et al., 2015). It is well known that addition of gums/hydrocolloids also improves the functionality of starch by altering its rheological/structural
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and gelatinization properties (Chaisawang and Suphantharika, 2006; Qiu et al., 2015; Chranioti et al., 2015 ; Lomeli Ramirez et al., 2014). In addition, gums can improve starch’s moisture content, water holding capacity and overall product quality without adding much calorific value
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(Funami et al., 2005; Choi et al., 2006; Arismendi et al., 2013; Nwokocha and Williams., 2014;
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Fadavi et al., 2014 ).
In the baking industry, it is more advantageous to use starch from tapioca than from other sources. Due to its clear paste with a bland taste and relatively high viscosity, TS has widespread usage in the food industry including bread, cakes, extruded cereals, beverages, sauces, and pie fillings in its gelatinized form (Chaisawang and Suphantharika, 2006). Native (unmodified or pure) starches have many undesirable properties such as low water holding capacity, retrogradation and syneresis (Wang et al., 2009; Zhu, 2015). These undesirable properties of
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native starch can be rectified either by modification or by the addition of gums (food hydrocolloids). Generally, Gums have benefits over the modification process because of their non-calorific value (calorie free) as well as better retainment of texture and stability during
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processing (Shi and BeMiller, 2002). These advantages have led to widespread usage of starch and gum combinations in a variety of food products (Kayacier and Dogan, 2006; Barros
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Fernandes et al., 2014; Gul et al., 2014; Ladjevardi et al., 2015).
Starch and gum combinations have been studied by many investigators. Chaisawang and
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Suphantharika (2006) studied the effect of the addition of xanthan gums on swelling, gelatinization and freeze-thaw stability of TS. They found that TS granules were completely wrapped by a tight adhering of xanthan gum, which caused their delayed swelling and retardation of gelatinization. In a very recent study, addition of gum arabic (GA) into a TS suspension showed a reduction in swelling power, solubility index and peak viscosity, which
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states that GA can be used as a stabilizer and viscosity controlling agent in the food industry (Chen et al., 2015). On similar lines, synergistic interactions between starch and gums have been
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studied by many researchers (Feng et al., 2012; Qiu et al., 2015; Chranioti et al., 2015; Chivero et al., 2016; Sanz et al., 2016).
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Although the modification of these food macromolecules by physical (thermal/nonthermal processing) and chemical means can also achieve some of the above mentioned objectives, these methods are not cost effective (Lee et al., 2005; Singh et al., Hong et al., 2016; Singh et al., 2014; Flores et al., 2010; Ahmed et al., 2014; Wongsagonsup et al., 2014; Singh et al., 2015, Ramaswamy et al., 2015) and the chemical modification is not considered natural. Therefore, it
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is of considerable practical importance to understand the role of gum interactions on the rheological properties of starch pastes.
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GA is commonly used as a stabilizer in the food industry. It is a weak polyelectrolyte that carries carboxyl groups and can be used as a source of dietary fiber (Nasir et al., 2008; Chen et al., 2015). The addition of GA to potato starch has been shown to lower the peak viscosity (Lee
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et al., 2002). In a similar study by Chen et al. (2015), GA was found to lower the peak viscosity and swelling power leading to a delay of retrogradation. These aspects can be attributed to many
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factors including molecular structure, interaction of amylose and amylopectin and ionic charges of starch and hydrocolloids (Sudhakar et al., 1996; Sanchez et al., 2002; Chaisawang and Suphantharika, 2006; Yadav et al., 2007; Ma et al., 2015)
Despite several studies done on the effect of gum on the starch properties, the effect of GA on
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the rheological, swelling and pasting behavior of native TS has not been investigated. Thus, the aim of the present study was to investigate the beneficial effect of GA on the swelling power (SP), solubility index (SOL), pasting, viscoelastic characteristics and flow behavior of native
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tapioca starch.
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2. Materials and Method
2.1. Materials
A native tapioca starch (TS) was bought from a local store with average particle size 10–15 µm; moisture content 12.8 ± 0.2%; ash content <0.5%; fat content <0.15%; and protein content 0.5%.. The starch was used as received, and their proximate composition (dry weight basis) mentioned above was provided by the manufacturer. Starch samples were verified for moisture
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content by a hot air oven drying method at 130°C until a constant weight was obtained in triplicates. The observed moisture content data varied from the supplier data by less than 1%.
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Gum arabic (GA) was purchased from Fischer Scientific
2.2 Viscoelastic dynamic rheometry:
The dynamic viscoelastic properties of TS and TS-GA mixtures were measured in triplicate
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using a controlled stress rheometer (AR 2000, TA Instruments, New Castle, DE, USA). A parallel-plate 60 mm geometry with a gap of 1 mm was used. To obtain a linear range for the
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dynamic analysis, the linear region was found at a strain of 2%, and a strain of 0.5 % was used to keep the tests in that region. A solvent trap with mineral oil was used to minimize water loss during the measurement. Frequency sweep tests (0.01–10 Hz) were carried out in the linear regime, at constant strain (0.5%) at 25◦C. All the rheological measurements were performed in
Rheology software.
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triplicate, and rheological parameters (G′, G″) were obtained directly from the TA Advantage
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2.3 Steady state characterization:
The steady flow measurements were performed on the same sample to obtain shear rate versus
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shear stress (flow curves) data. The 2 degree 60mm plate was programmed to ramp the shear rate from 0.1 to 100 s−1 in duplicates. Data from the samples was used to estimate the fit of this data to the power law using the following equation: σ = Kγn
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where σ is the shear stress (Pa), γ˙ is the shear rate (s−1), K is the consistency coefficient (Pa sn), and n is the flow behavior index (dimensionless).
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2.4 Pasting properties:
Pasting properties of TS and TS-GA mixtures were determined by a starch pasting cell attachment on the TA rheometer (AR 2000, TA Instruments, New Castle, DE, USA). The
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mixtures were made by first dispersing GA in water at concentrations of 0.1. 0.3, 0.6 and 1.0% (w/w) with magnetic stirring, and then starch (5%) was added to the gum solutions. The TS was
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added slowly to the mixtures with stirring to avoid any lump formation. These TS-GA mixtures were poured into the starch pasting cell for measurement of pasting properties. The samples were first stirred (100 s-1) for 10 s at 30°C, and then the shear rate was held at 30 s-1 until the end of the test. The sample was heated from 30°C to 95°C at 15°C /min and the temperature was held
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at 90°C for 5 min. Afterward, the sample was cooled to 30°C at 15°C/min and held at 30°C for 5 min. TA Instruments rheology data analysis software was used for calculating the following parameters: pasting temperature (PT): the temperature at which viscosity starts to rise; peak
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viscosity (PV); the highest viscosity recorded throughout heating; hot paste viscosity (HPV): the viscosity value at the end of the isothermal period at 90°C; and cold paste viscosity (CPV): the
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viscosity value at the end of the isothermal period at 30°C (Martínez-Cervera et al., 2014).
2.5. Swelling power and solubility index:
Swelling power (SP) and solubility index (SOL) were determined using the method of Leach, McCowen, and Schoch (1959) with some modification. Starch dispersions were centrifuged and heated in a water bath at temperatures of 90°C for 5 minutes. The average heating rate as
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recorded by thermocouples placed in tubes was 18°C/min. Constant stirring was applied in order to prevent any sedimentation. After heating, samples were centrifuged (3000 rpm, 15 min). The precipitated paste was separated from the supernatant and weighed (Wp). Both phases were dried
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at 105°C for 24 h and the weight of dry solids in precipitated paste (Wps) and supernatant (Ws) were calculated. SP is the ratio of the weight of swollen starch granules after centrifugation (g) to
(hydrated starch granules (g) /dry granules in precipitated paste (g))
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SP =
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their dry mass (g).
(1)
The SOL is the percentage of dry mass of solubles in the supernatant (Ws) to the dry mass of whole starch sample (W0).
100% (soluble solids (g) / whole starch sample (g))
2.6 Statistical analyses:
(2)
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SOL =
The experiment consisted of two full treatment replications, while individual replicate analyses
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of the film were conducted at least in duplicate. Statistical analyses were carried out by the
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analysis of variance (ANOVA) using SAS 9.2 software (SAS Institute, Cary, NC, USA). Duncan's multiple range test (p < 0.05) was used to determine the statistical differences among the mean values.
3. Results and Discussion
3.1 Pasting properties:
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This study was the first of its kind to evaluate the impact of gum arabic (GA) with increasing concentration on pasting properties of tapioca starch (TS) system. Different parameters were measured to compare the peak viscosity (PV), hot paste viscosity (HPV), cold paste viscosity
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(CPV), relative breakdown (RB) and total setback (TSB). It has been observed by many investigators that addition of hydrocolloids alters the pasting properties of starch. This study has very clearly demonstrated that addition of GA results in a significant (P<0.05) decrease in PV,
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RB, and TSB values (Table 1). The GA presumably covered most of the TS granules and promoted granules association, which restricted swelling of the granules and limited the increase
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in viscosity during pasting. The addition of GA into TS had an antagonistic effect as it caused a decrease in PV of the biphasic TS-GA system. A similar trend was reported, which showed a reduction of PV, RB, and TSB viscosities upon addition of xanthan gum into tapioca starch (Chaisawang and Suphantharika, 2006). One of the possible reasons for delay in pasting and
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reduction in PV was retardation of granule destruction and leaching of amylose, when negatively charged starch solution were heated with anionic gums, as explained in detail by Shi and BeMiller (2002). They also explained that such effects were due to interactions between leached
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amylose molecules and gums used.
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The GA utilized in this experiment had a low molar mass (1.86 × 105 g mol−1), which was comparatively lower than some other polysaccharides (Renard et al., 2012.) It was found that most of the hydrocolloids increase the viscosity but the hydrocolloids with lower molecular mass may lead to a decrease in the viscosity as described in the case of corn fiber gum and guar gum (Qiu et al., 2015b; Funami et al., 2005b), which may be useful in terms of controlling viscosity of emulsion/mixture/dispersions. In a similar study, it was found that the main reason for the decreased viscosity was the lower molar mass of guar gum (4.7 x 105 g mol−1) as described by
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Funami et al. (2005b). They explained that the lower molecular mass of guar gum produced a smooth flow and prevented the abrasion of starch granules without interacting with amylose or
start to rupture and breakdown leading to a PV decrease.
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amylopectin leaching. When a starch suspension reaches its maximum viscosity, its granules
Heating of a TS-GA system leads to gelatinization of the starch granules, which in turn increases
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the viscosity of the overall system. The main reason for such behavior is that the gum arabic (GA) is located in the continuous phase and its concentration is increased as the volume of the
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starch phase accessible to GA is reduced due to swelling during gelatinization (Alloncle et al., 1989). This increase in viscosity is mainly due to swollen granules and when shear forces are exerted, it results in the loss of granule integrity and further disruption leading to an increase in the paste viscosity. This later phenomenon is defined as breakdown viscosity and is clearly seen in the TS-GA interactions in the present study, which agrees with other investigator’s findings
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for starch and gum mixtures (Christianson et al., 1981; Ahmed et al., 2014; Qiu et al., 2015a).
The change in the PV during heating (Table 1) clearly indicated that there was starch
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gelatinization upon heating. It was also visible that there was a strong impact of the addition of GA to the TS dispersion. The peak viscosity decreased from 0.052 to 0.038 Pa.s after the
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addition of 1.0% GA. There was a gradual decline in the PV with increasing concentration of GA from 0.1 to 1.0%.
Relative breakdown (RB) was used instead of traditional breakdown to quantify the degree of the starch structure change. There was a gradual increase (-0.2456 to -0.1316) in the RB values by increasing the concentration of GA (0.0 to 1.0%) in the TS-GA mixture. Relative breakdown (RB) gives the degree of starch structure breakdown during cooking and has the advantage of
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eliminating the differences attributed to different initial PV values, allowing correct comparison among different samples. The total setback (TSB) is the final increase in the viscosity during the cooling phase which is related to the retrogradation phenomenon. The effect on TSB was
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markedly visible (decreasing from 0.037 to 0.017) with increasing concentration of GA from 0.11.0%. TSB values of TS-GA dispersions decreased by a factor of more than ½ with increasing concentration of GA from 0.1 to 1.0%. The TS-GA interaction can be influenced by a number of
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factors including amylose content, length of amylose molecules and the state of dispersion of the
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amylose chains (Chaisawang and Suphantharika, 2005; Singh et al., 2010).
3.2 Flow behavior
The dispersion of TS-GA mixtures was evaluated at 25◦C for determining their rheological behavior. The shear stress- shear rate graphs show that increasing concentration of gum arabic in
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the TS-GA mixtures from 0.1 to 1.0% lead to an increase in the flow behavior (Figure 1). When the shear rate and the shear stress data were fitted to various models, these TS-GA mixtures data fitted well to the power law with high regression coefficient (R2 ≥0.93) (Table 2). Newtonian
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fluids have flow behavior of 1 and values lesser than 1 are considered non-newtonian (pseudoplastic behavior) (Lu et al., 2012; Ahmed et al., 2014). In the present study, (control) TS
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and all TS-GA mixtures were found to show pseudoplastic behavior. The flow behavior index (n value) of TS-GA mixture was found to consistently decrease from 0.47 to 0.23 with increasing concentration of GA from 0.1-1.0%. The control TS sample was a mixture of starch and water which exhibited shear thinning behavior very similar to that of the TS-GA mixtures (Table 2). An increase in the pseudoplasticity might be due to the higher degree of structural breakdown during shearing at higher GA concentration in the TS-GA mixture. A similar trend was also
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found by Chen et al., 2015, where the addition of Gum arabic to the Tapioca starch led to the lower value of the n index.
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The consistency coefficient (k) acts as an indicator of viscosity and was determined from the flow data. The mixture of TS-GA with the highest concentration of GA (1.0 %) showed a k value of 0.283, which was almost 50 times greater than TS control (k value =0.006). The consistency
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coefficient (k) showed a consistent increase following the increasing trend of GA percent concentration (i.e. 1.0>0.6>0.3>0.1>control). It has been found that an increase in the
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concentration of GA causes an increase in intermolecular interactions or entanglement which leads to increase in consistency coefficient (Chen and Chen, 2001). Flow index (n) and consistency coefficient (k) show that the changes in the flow properties of TS-GA mixtures are highly dependent on the GA concentration.
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Although the concentrations of GA in the TS-GA mixture were low, the apparent viscosity (η10) of the mixture was highly affected (0.005 to 0.048 Pa-s) with increasing concentration (0.1 to 1.0 %) of GA (Table 3). All the samples including control showed non-Newtonian behavior as the
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η10 decreased with increasing shear rate (Figure 2). The η10 value of the control sample (0.005) increased three times to 0.018 by addition of just 0.1% GA. These results demonstrate for the
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first time, that addition of a small amount of GA (even 0.1%) caused a major change in the η10 apparent viscosity of the TS-GA mixture.
Similar trends were observed for the tapioca starch- gum arabic (Chen et al., 2015) and corn fiber gum-maize starch (Qiu et al., 2015a). The increase in the η10 of TS-GA suspensions might be due to a synergistic effect of GA. Similar increases in the viscosity of many cationic, anionic and neutral polysaccharides by interaction with corn fiber gum (CFG) have been reported (Zhang et
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al. 2015) and it has been interpreted that it was due to the synergistic effect of CFG on the polysaccharides studied. The increase in η10 has also been reported for other gum and starch
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systems and was thought to be due to their physical interactions (Warrand et al., 2005).
3.3 Viscoelastic characterization
Viscoelastic properties are used for the viscous and elastic characterization of food samples
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(Kealy, 2006; Ahmed et al., 2015). The control TS and TS-GA dispersions were studied in terms of rheological changes by employing the frequency range of 1-10 Hz. There was an increasing
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trend in the viscoelastic properties (G”, G’ & tan δ) with increasing frequency from 0.1-10 Hz (Figures 3, 4 and Table 3). The rheological properties analysis showed a greater structural rigidity as indicated by the increase in G′ and G″ values with increasing concentration of GA in the mixtures (Table 3). There was a significant frequency dependency of the dynamic moduli for
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all TS-GA mixtures. This suggests that there was a strong interaction between GA and TS amylose in the composite system. The higher the frequency, the more was the mixture elasticity (G′>G″) in the studied frequency interval. Viscoelastic characterization indicates that addition of
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GA leads to a predominantly elastic behavior (Table 3). These results clearly indicate that the
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GA-TS mixtures are in the weak gel category (Clark and Rosse Murphy, 1987; Qiu et al., 2015)
The control sample containing 5% TS showed a very similar behavior like TS-GA mixtures in terms of viscous and elastic behavior with increasing frequency, but the elastic modulus G’ was predominant over the viscous modulus G" at both low and high frequencies (Table 3). With the addition of GA to TS and its increasing concentration from 0.1 to 1.0%, there was a corresponding increase in both the viscous and the elastic moduli (G’ and G”). However, when the concentration of GA in the TS-GA mixture was near the lower end (0.1-0.3%), the amount of
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increase in the G’ and G” values was small. But when the concentration of GA in the TS-GA mixture was near the higher end (0.6-1.0%), there was a significant increase (about 3 to 4 times) in the G’ and G” values (Table 3). These results clearly indicate that the extent of viscoelastic
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properties, especially elasticity was higher at the higher concentration of GA used. Similar results were reported on a maize starch – flaxseed gum mixture study, where the G’ value was nearly an order of magnitude higher than the G” value in the experimental range for all samples
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(Mohammed et al., 1998). The tan δ is an indicator of viscoelastic properties and is the ratio of G’ and G”. The tan δ values were changed by addition of GA . At lower concentrations of GA in
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the TS-GA mixtures (0.1-0.3%), tan δ gradually increased by 70% showing a more liquid-like behavior. However, at higher GA concentrations (0.6-1.0%), there was a decreasing pattern of tan δ values showing that the TS-GA mixtures had a more solid-like behavior than the control TS. There is a possibility of a threshold level after 0.3% concentration as the tan δ plummeted
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above this concentration.
3.4 Swelling power and solubility index:
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The gelatinization process leads to the swelling of the starch granules, which then ruptures and amylose leaches out of the granules. The amount of swelling of starch granules by the
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gelatinization process is dependent on its amylopectin content, but its amylose acts as a swelling inhibitor (Chaisawang and Suphantharika, 2005; Hong et al., 2016).
Swelling power (SP) and solubility index (SOL) were determined following the method of Mandala and Bayas, 2004. It has been generally observed that upon heating of starch suspensions, the starch granules imbibe quickly and rupture due to disruption of amylopectin double helices (Biliaderis, 2009). Swelling is considered as a two stage process: an initial slow
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process followed by a faster one afterward (Kokkini et al., 1992; Mandala and Bayas, 2005). Swelling power of tapioca starch (TS) was found to have a SP value of 1.29. Upon addition of GA and increasing its concentration, there was no systematic effect observed for the SP. There
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were changes with the addition of GA, but the changes were insignificant (P<0.05). The SP behavior of the TS-GA mixtures followed a trend similar to peak viscosity (PV) shown in Tables 1 & 4. In a similar study, when guar or xanthan gum was added to native tapioca starch, the SP
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of native starch–xanthan gum mixture was almost unchanged (Chaisawang and Suphantharika, 2006). This was due to the restricted swelling of the starch granules caused by the tightly
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wrapped xanthan gum layer. This current study showed similar results to that of above cited study of Chaisawang and Suphantharika, 2006. It is generally known that a small increase in the SP is also marked by a small decrease in peak viscosity (PV) during starch pasting as evidenced in Table 4. Mandala and Bayas, 2004 found a very similar trend in their study when xanthan
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gums were added to starch mixtures. However, different trends were observed for SOL. Control TS had a SOL value of 178.4, which almost doubled to 365 with the addition of only 0.1% GA. By increasing the concentration of GA from 0.1 to 1.0%, a further increase in SOL value from
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365 to 665 was observed. The TS-GA mixture showed the following increasing trend in SOL: TA+GS 1%> TA+GS 0.6%> TA+GS 0.3 %> TA+GS 0.1%> control TS with the addition of
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GA. These differences in swelling power may be attributed to the differences in amylose content, viscosity patterns and weak internal organization resulted from negatively charged groups within the starch granules (Singh et al., 2003). By increasing the concentration of gum arabic in GA-TS mixture, there was an increase in the swelling of granules during heating and many large granules were observed even at relatively low temperature (75 °C). Amylose leakage increases also during heating until 85°C which acted as a restricting temperature. Due to gum arabic
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effects on granules swelling and SOL, it was visible that the viscosity and consistency of GA-TS mixture heated together at 75 °C would be relatively high.
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3.5 Relationship between rheological, thermal and functional properties The effect of gum arabic on the functionality of tapioca starch has been explored by determining the following properties: rheological, thermal and functional properties. A correlation between
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viscoelastic parameters (G′, G′′) and apparent viscosity (ɳ10) was found. The strong increase in elastic and viscous modulus of TS-GA mixture correlates well with apparent viscosity (Table 3).
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Similarly, the solubility show a strong correlation with the consistency coefficient and it was found that both of these characteristics increased many folds with increasing concentrations of gum arabic. Flow behavior showed a decreasing n value which indicates pseudoplastic behavior upon shearing. This pseudoplastic behavior showed a similar trend to that of pasting behavior.
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Pasting values such as peak viscosity and HPV showed a trend similar to that of the flow behavior index, which indicates that upon heating and shearing, the mixture of GA and TS might show a similar effect. Swelling power (SP) and solubility (SOL) can be used to assess the extent
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of interaction between starch chains, within the amorphous and crystalline domains of the starch granule (Ratnayake et al., 2002). The ability of starches to swell in excess water and their
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solubility also differed significantly as solubility and swelling properties showed entirely different trends (Table 4). Due to the capability of adsorbing more water, increasing concentration of gum arabic in the tapioca starch showed increasing tan δ, and exhibited more liquid phase as indicated by high tan δ. Interrelationship between swelling power and peak viscosity during pasting behavior was observed. These results are consistent with previously reported findings on interactions between starch and gums (Chaisawang and Suphantharika, 2005; Chaisawang and Suphantharika, 2006; Chen et al., 2015).
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Conclusion
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Currently, there is trend in market towards clean label food, which implies no chemical modifications. The addition of gum arabic (GA) to native tapioca starch (TS) improved its pasting, rheological properties, and functionalities (swelling power and solubility index). But
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there was no particular trend in the swelling power of TS with the addition of GA. The viscoelastic properties were found to increase with increasing concentration of GA with elastic
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modulus slightly higher than the viscous modulus. The flow behavior index showed pseudoplastic behavior with increasing concentration of GA in the TS-GA mixture. Nevertheless, the consistency coefficient increased almost 5 times from the control sample to the TS-GA sample with 1% GA. A strong relationship was noticed between solubility index and G”
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on the addition of GA to TS composite. Thus, it can be concluded from these results that GA can modify a native starch giving a more solid like rheological behavior by strengthening its network structure. Therefore, clean label gums can be used to improve functioanlity of the starches
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without any chemical modification.
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Acknowledgements
This research was supported in part by an appointment to the ARS Research Participation Program administered by the Oak Ridge Institute for Science and Education (ORISE).
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(2015).
Composition,
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227.Zhu,
structure,
physicochemical
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modifications of cassava starch. Carbohydrate polymers, 122, 456-480.
properties,
and
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Tables Table 1. Pasting properties of tapioca starch and its mixture with various concentrations of gum
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arabic.
Peak Vis (Pa.s)
HPV*
CPV**
(RB)
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Conc.
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Relative breakdown
Total setback (TSB)
[(PV-HPV)/PV]
CPV- HPV
0.052
0.064
0.11
-0.246
0.037
5%TS+0.1 GA
0.058
0.070
0.11
-0.207
0.040
5%TS+0.3 GA
0.054
0.061
0.09
-0.220
0.029
5%TS+0.6 GA
0.050
0.062
0.09
-0.170
0.028
0.043
0.06
-0.132
0.017
EP 0.038
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5%TS+1.0 GA
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5 % TS
* Hot paste viscosity
** Cold paste viscosity
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Table 2. Flow properties of tapioca starch and its mixture with various concentrations of gum arabic
n
k( Pa.sn)
5% TS
0.990±0.01
0.006±0.001
0.99
5% TS + 0.1% GA
0.470±0.01
0.063±0.001
0.98
5% TS + 0.3% GA
0.330±0.01
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0.129±0.020
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5% TS + 0.6% GA
5% TS + 1.0% GA
0.201±0.010
0.96
0.235±0.01
0.283±0.010
0.95
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0.93
0.296±0.02
K, consistency coefficient (Pa.sn); n, flow behavior index (dimensionless).
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Mixtures
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G'
G'
10 rad/s 10 rad/s 50 rad/s 50 rad/s
0.110
0.087
5%TS+0.1% GA
0.133
0.119
3.740
5%TS+0.3% GA
0.145
0.216
5%TS+0.6% GA
0.713
0.291
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0.991
1.689
1.364
0.296
ɳ10 (Pa-s)
tan δ
10 s-1
10 s-1
0.005
0.792
1.220
0.018
0.889
2.580
2.544
0.027
1.487
4.543
3.540
0.039
0.408
8.990
3.784
0.048
0.299
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5% TS
5%TS+1.0% GA
G"
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Samples
G"
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Table 3. Apparent viscosity (η10) at 10 s-1 & viscoelastic parameters (G’, G”) at low and high frequencies (10 & 50 rad/s) using different TS-GA concentrations at 25°C.
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Table 4. Swelling power (SP) and solubility index (SOL) as affected by addition of gum arabic
Concentration
swelling power SP
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to tapioca starch.
SOL
1.29 ± 0.05
178.40 ± 1.52
5%TS+0.1% GA
1.24 ± 0.02
365.67 ± 2.25
5%TS+0.3% GA
1.23 ± 0.03
5%TS+0.6% GA
1.30 ± 0.03
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477.42 ± 4.25 584.21 ± 2.58
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5%TS+1.0% GA
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5% TS
665.47 ± 3.58
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Figures
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2.250
2.000
5% TS +0.1% GA 5%TS +0.3% GA 5% TS+0.6% GA 5%TS+1% GA 5% starch only
1.250
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shear stress (Pa)
1.500
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1.750
1.000
0.7500
0.2500
0 10.00
20.00
30.00
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0
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0.5000
40.00 50.00 60.00 shear rate (1/s)
70.00
80.00
90.00
100.0
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Figure 1: Effect of increasing concentration of gum arabic on flow behavior (shear stress/ shear rate curve) in the TS-GA mixture
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Shear rate (1/s) 0
10
20
30
40
50
60
70
80
90
0.5
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0.05
5% TS +1.0% GA
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Apparent Viscosity )Pa.s)
5% Starch
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0.005
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Figure 2: Rheogram representing the change in apparent viscosity of TS-GA mixture as a function of shear rate
100
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10.00
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G' (Pa)
1.000
0.1000
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0.01000
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5% starch, Frequency sweep step 5%TS-1, Frequency sweep step 5%TS-0, Frequency sweep step 5%TS- , Frequency sweep step 5%TS &0, Frequency sweep step
1.000E-3 0.1000
1.000 frequency (Hz)
10.00
Figure 3: Effect of increasing concentration of gum arabic on elastic modulus (G’) in the TS-GA
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mixture
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10.00
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G'' (Pa)
1.000
0.1000
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0.01000
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5% starch, Frequency sweep step 5%TS-1, Frequency sweep step 5%TS-0, Frequency sweep step 5%TS- , Frequency sweep step 5%TS &0, Frequency sweep step
1.000E-3 0.1000
1.000 frequency (Hz)
10.00
Figure 4: Effect of increasing concentration of gum arabic on viscous modulus (G”) in the TS-
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GA mixture
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Highlights
1. Gum Arabic can used to improve functionality of this native starch.
3. Gum arabic improves functionality of native tapioca starch. 4. Gum arabic and tapioca starch gives highly viscous gels.
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2. Gum arabic has an advantage of being clean label, cheaper, less calorific value.
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5. These gels will open up new avenues of gums in the starch application market.