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Food Chemistry 202 (2016) 3139

Contents lists available at ScienceDirect

Food Chemistry
journal homepage: www.elsevier.com/locate/foodchem

Effects of waxy rice and tapioca starches on the physicochemical


and sensory properties of white sauces enriched with functional fibre
_
Grazyna Bortnowska a,, Agnieszka Krudos b, Violetta Schube c, Wioletta Krawczynska b,
Natalia Krzeminska a, Katarzyna Mojka a
a
Department of Food Technology, West Pomeranian University of Technology in Szczecin, Poland
b
Center of Bioimmobilisation and Innovative Packaging Materials, West Pomeranian University of Technology in Szczecin, Poland
c
OHLY GmbH, Hamburg, Germany

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

Article history: This study was conducted to examine the physicochemical and sensory properties of gluten-free white
Received 1 July 2015 sauces (WSs) prepared with waxy rice starch (WRS) or tapioca starch (TS) and high amylose maize starch
Received in revised form 2 December 2015 (HAMS) as the source of resistance starch RS2 type. HerschelBulkley model (HB) was successfully used
Accepted 19 January 2016
to describe the flow behavior of WSs. Temperature had a notable effect on the derived from HB relation
Available online 20 January 2016
parameters and the Arrhenius equation was applied to describe changes in consistency. The values of
storage modulus (G0 ) were higher than those of loss modulus (G00 ) with loss tangent between 0.1 and
Chemical compounds studied in this article:
1.0 within the tested frequency range of 0.150 Hz. Generalized CoxMerz rule was used to correlate
Potassium sorbate (PubChem CID:
23676745)
the steady shear properties to viscoelasticity of WSs. Consumers were tolerant to the presence of
Sodium chloride (PubChem CID: 5234) HAMS and mostly interested in consuming WSs containing 3.03.5 wt% WRS and 2.53.0 wt% TS.
2016 Elsevier Ltd. All rights reserved.
Keywords:
White sauce
Starch
Functional fibre
Rheology
Sensory analysis

1. Introduction interface and forming interfacial films with different characteristics


(Singh & Sarkar, 2011). Moreover, MPs have physiological impor-
White sauces (WSs) are multicomponent systems which can be tance, they facilitate uptake of several essential nutrients such as
considered as low-fat oil-in-water emulsions containing other types trace elements and vitamins, in addition some of them perform a
of suspended particulates, such as thickeners and spices. They are protective function indicating their multifunctional properties
commonly employed and consumed by many groups of consumers (Nagpal et al., 2011). Whereas, flours and starches are generally
including children and elderly people in an almost daily basis used to control structure, texture and stability of sauces because
(Arocas, Sanz, & Fiszman, 2009). However, manufacturing of they enhance thickness and viscosity of the continuous phase
gluten-free (G-F) sauces can be nowadays of great interest, because inhibiting the tendency of the dispersed phase to migrate and floc-
G-F diet is essential for patients having gluten-sensitive enteropa- culate or coalesce (Bortnowska et al., 2014; Chuah, Kuroiwa,
thy or celiac disease and number of diagnosed patients with these Kobayashi, & Nakajima, 2014). It should be also highlighted, that
illnesses in the recent years has considerably increased (Torres, in complex systems, such as food emulsions, there may be synergis-
Fradinho, Raymundo, & Sousa, 2014). The basic ingredients of WSs tic or antagonistic interactions between different kinds of biopoly-
are: milk, oil, flour or starch, salt and spices (Guardeo, Hernando, mers and other components that induce changes in their
Llorca, Hernndez-Carrin, & Quiles, 2012). Milk proteins (MPs), in functional properties and consequently may affect physicochemical
both soluble and dispersed forms, have been known to be excellent characteristics of the final product (McClements, 2006).
emulsifiers because of their amphiphilic nature. MPs exhibit good The increasing consciousness of the consumers that food may
surface-active properties by reducing the tension at the oilwater promote human health and well-being has encouraged many food
developers and researchers to functionalize products beyond its
mere nutritional value (Betoret, Betoret, Vidal, & Fito, 2011). For
Corresponding author. example, there is existing strategy to increase fibre consumption
E-mail address: Grazyna.Bortnowska@zut.edu.pl (G. Bortnowska). of the general population by enriching products with a high

http://dx.doi.org/10.1016/j.foodchem.2016.01.077
0308-8146/ 2016 Elsevier Ltd. All rights reserved.
32 G. Bortnowska et al. / Food Chemistry 202 (2016) 3139

frequency of consumption (Ares, Baixauli, Sanz, Varela, & Salvador, 2.3. Stability test
2009). For this reason, WSs could be the interesting products to
incorporate dietary fiber such as resistant starch (RS) that recently Physical stability of the white sauces (WSs) was evaluated using
has gained attention due to its beneficial physiological and protec- accelerated ageing test. Aliquots (8.0 ml) of the WSs were trans-
tive effects associated e.g. with preventing the development of ferred to the 10 ml test tubes and centrifuged at 2400 g for 15 min,
abnormal cell population as well as reduction of glycemic index. applying a MPW 350 centrifuge (Med.-Instruments, Warszawa,
RS is generally considered of four types, between them the RS2 rep- Poland). The stability index (SI) of WSs was calculated from equa-
resents starch that is in a certain granular form and resistant to tion: SI% HC
HT
 100, where: HC, height of creamed layer and HT,
enzyme digestion (Sajilata, Singhal, & Kulkarni, 2006). The literature initial sauce height.
search revealed that the number of studies regarding complex
physicochemical properties of white sauces prepared with gluten-
2.4. Color assessment
free thickeners, particularly starches with different amylose/amy-
lopectin ratio, is generally limited and those dealing with white
Color of the white sauces was measured with a HunterLab
sauces containing RS2 have not been found.
Model D25-2A Digital Color Difference Meter (Hunter Associates
The objective of this research was to investigate the influence of
Laboratory Inc., Fairfax, VA, USA) at 2 view angle. The calibration
waxy rice and tapioca starches belonging to the Novation class on
was done with a white C2-6544 plate (X = 86.30, Y = 88.51,
the stability, rheological and sensory properties of white sauces
Z = 101.99). Color coordinates were expressed as: lightness (L),
supplemented with RS2.
redness/greenness (+/ a) and yellowness/blueness (+/ b).
Experimental data were characterized in terms of whiteness index:
WI = 100  [(100  L)2 + a2 + b2]1/2, hue angle: Ho = tg1 (b/a)
and chroma: C = (a2 + b2)1/2.
2. Materials and methods

2.5. Scanning electron microscopy (SEM)


2.1. Materials

The microstructure of white sauces (WSs) was determined


Functional native waxy rice starch (WRS) NovationTM 8300
using Vega-3 LMU scanning electron microscope (Tescan, Czech
(12.8 wt% moisture, 4.8 wt% amylose, 0.5 wt% proteins, 0.2 wt%
Republic) according to the procedures of Chen, Zhang, and Zhong
fat), organic food starch refined from tapioca (TS) NovationTM
(2015) with modifications. The WSs were diluted (1:8) with dis-
9360 (13.1 wt% moisture, 19.6 wt% amylose, 0.4 wt% proteins,
tilled water and then the samples were stuck onto a cylindrical alu-
0.15 wt% fat), highamylose maize starch (HAMS) as a source of
minum stub with a double-sided tape. Subsequently, the samples
resistant starch type 2 (RS2) Hi-MaizeTM 260 (12.3 wt% moisture,
were dried at 50 C for 6 h in a convection drying oven (Binder
70 wt% amylose, 60 wt% total dietary fiber, 46 wt% RS2, 0.8 wt%
FD 53, Binder GmbH, Germany). Prior to SEM inspection, samples
proteins, 0.8 wt% fat, 1015 lm particle size) were donated by
were coated with a thin layer of gold using a sputter coater
Ingredion GmbH (Hamburg, Germany). Potassium sorbate and
(Q150T ES, Quorum Technologies Ltd, United Kingdom) and trans-
sodium chloride were obtained from Hartim (Szczecin, Poland).
ferred into the scanning electron microscope operating at an accel-
Rapeseed oil (7 wt% saturated, 65 wt% monounsaturated and
erating voltage of 10 kV.
28 wt% polyunsaturated fatty acids), powdered milk (10.4 wt%
moisture, 37.5 wt% proteins, 51.2 wt% carbohydrates, 0.8 wt%
fat), ground black pepper fruits (Piper nigrum L.) and nutmeg were 2.6. Determination of rheological properties
bought from a local retailer.
The rheological properties of the white sauces were evaluated
using a strain/stress controlled AR-G2 rheometer (TA Instruments,
New Castle, DE, USA), equipped with a coneplate geometry
2.2. White sauces preparation (2Cone angle, 60 mm diameter, 62 lm gap) and a Peltier heating
system. All rheological data were recorded with the TA Rheology
Powdered milk was mixed (250 rpm, 10 min) with distilled Advantage Data Analysis equipment software V5.4.8. The steady
water (85 C) using a MSM 66120 blender (Bosh, Germany) and shear tests were performed to obtain shear stress data versus shear
the resulted milk was stored at 4 C overnight to ensure complete rate at temperatures ranged from 20 C to 80 C. The shear rate was
hydration of milk proteins. Then, milk was homogenized with programmed to increase from 0.1 s1 to 300 s1 followed by the
rapeseed oil at 7000 rpm for 20 s using a laboratory-scale T 18 reduction from 300 s1 to 0.1 s1. Data from the ascending seg-
basic Ultra-Turrax package homogenizer (IKA Werke GmbH Co. ment of the shear cycle were fitted to HerschelBulkley (HB)
KG, Germany). Next, appropriate amount of starches: waxy rice model: r = r0 + kc_ n , where: r, shear stress (Pa); r0, yield stress
starch (WRS), tapioca starch (TS) and high-amylose maize starch (Pa); k, consistency coefficient (Pa sn); c_ , shear rate (s1) and n, flow
(HAMS) were added and the systems were heated in a water bath, behavior index (). The time-dependent rheological properties
to 90 C (5 C/min) at stirring speed of 1500 rpm. Subsequently, were examined by measuring areas of hysteresis loops and shear
required quantities of sodium chloride (NaCl), ground black pepper stress decays. The percentage of relative hysteresis area (Ar%)
fruits (GBP), potassium sorbate and nutmeg were put into the was calculated from the equation: Ar (%) = [(Aup  Adown)/Aup] 
sauces and they were kept at 90 C for 20 min under mild agitation. 100, where: Aup and Adown, areas enclosed by the upward and
Finally, the white sauces (WSs) contained constant amount of: downward flow curves (Pa s1), respectively. The shear stress
rapeseed oil (3.0 wt%), powdered milk (10.0 wt%), HAMS (2.0 decay experiments were conducted in the time range of 0
wt%), NaCl (0.25 wt%), GBP (0.02 wt%), potassium sorbate (0.1 wt%) 60 min at constant shear rate of 100 s1 and determined values
and nutmeg (0.02 wt%), whereas WRS and TS ranged from 2.0 were evaluated applying Weltman model: r = A  B ln t, where:
wt% to 3.5 wt%. Freshly prepared WSs were cooled down to 4 C A, structural parameter (Pa) and B, coefficient of the thixotropic
in an icewater bath and kept for one day in a refrigerator (4 C). breakdown structure (Pa s1). The temperature dependence was
The experiments were performed at fixed temperature of 20 C evaluated by fitting experimental data to the Arrhenius-type equa-
unless otherwise stated. tion: k = k0 exp(Ea/RT), where: k0, Arrhenius constant (Pa sn); Ea,
G. Bortnowska et al. / Food Chemistry 202 (2016) 3139 33

activation energy (J mol1); R, gas constant (J mol1 K1) and T, 2.0 wt% TS, they were partly joined together, whereas in those
temperature (K), using k parameter as an indication of the viscous composed of 3.5 wt% TS just glued (Fig. 1C and D). There were dis-
nature of food. Frequency (x) sweeps in the range of 0.150 Hz tinctive differences regarding microstructure of membranes
were carried out at constant shear stress of 0.1 Pa and storage formed on the oil droplets. In WSs containing 2.0 wt% WRS the dro-
modulus (G0 , Pa), loss modulus (G00 , Pa), complex modulus: G plets surfaces were rough (Fig. 1A), whereas in those prepared with
(Pa) = (G0 2 + G00 2)1/2, loss tangent: tan d = G00 /G0 and complex viscos- 3.5 wt% WRS as well as 2.0 and 3.5 wt% TS the interfacial layers
ity: g (Pa s) = G/x, were thus obtained as a function of x. The G0 were very smooth and compact, most probably due to adsorption
and G00 moduli were modeled as power function using following of greater amount of starch components and formation two-
expressions: G0 = K0 xn , G00 = K00 xn , where: K0 , K00 (Pa sn , Pa sn )
0 00 0 00
layered interfacial membranes (Fig. 1B, C and D). Resistant starch
and n0 , n00 (), are consistency coefficients and behavior indexes, granules of highamylose maize starch (HAMS) were observed in
b
respectively. Generalized CoxMerz rule: g x Cfga c_  gxc_ , the SEM images as globular white particles, partly visible regarding
where: ga, apparent viscosity (Pa s) and C, b, constants, was used WSs prepared with 2.0 and 3.5 wt% WRS (Fig. 1A and B).
to establish relation between dynamic and steady shear rheologi-
cal data. Bohlins parameters were assessed from the equation: 3.2. Rheological properties
G = A x1/z, where: z, coordination number (dimensionless) and A,
proportional coefficient (Pa s1/z). The steady shear properties of white sauces (WSs) were investi-
gated over a wide range of temperature at 20, 40, 60 and 80 C and
the examples of flow curves determined at 20 C are presented in
2.7. Sensory evaluation
Fig. 2 A and B. For the range of shear rates used in this experiment
the WSs exhibited in majority qualitatively similar thixotropic (data
Sensory analyses of the white sauces (WSs) formulations were
not shown) shear-thinning with yield stress behavior and only flow
performed using effective acceptance and preference tests with
curve of sample containing 3.5 wt% TS showed an overshoot
110 untrained tasters (23 male and 87 female, aged 2126)
(Fig. 2B) that was not detected at higher studied temperatures. In
recruited among students of Food Technology Department, West
general the results are in good agreement with those reported by
Pomeranian University of Technology in Szczecin, Poland. The pots,
other researchers regarding dairy systems prepared with polysac-
labeled with three-digit random numbers were filled with 100 mL
charide thickeners (Bayarri & Costell, 2011; Guardeo et al.,
WSs and presented to the panelists at 50 C, i.e. at temperature
2012). The observed shear-thinning behavior of WSs may be attrib-
similar to what consumers would normally encounter. For each
uted to structural breakdown and evolution of the particles align-
sample, participants had to score its: appearance, flavor, texture
ment in the direction of flow followed by the decrease in physical
and overall acceptability using a 9-point hedonic scale: 1 = dislike
interactions between adjacent polymer chains (Hosseini-Parvar,
extremely, 5 = neither like nor dislike, 9 = like extremely. Mineral
Matia-Merino, Goh, Razavi, & Mortazavi, 2010). Whereas, the over-
water was used by the panelists to rinse the mouth between sam-
shoot may be considered that it reflects the stress that was needed
ples. The WSs were also evaluated for roughness, related to the
to break the very compact gelatinized structure of sample (Fig. 1D)
HAMS granules sensed on palate and tongue, using a scale 05,
and cause the solution to revert to its normal viscous flow
where 0 and 5 represented no roughness and the strongest rough-
(Santipanichwong & Suphantharika, 2009). Irrespectively of the
ness, respectively.
starch type, its addition moved the flow curves upwards, however
the increasing magnitudes in shear stress (apparent viscosity) were
2.8. Statistical analysis greater in tapioca starch (TS) than waxy rice starch (WRS) based
sauces (Fig. 2A and B). The found results may be postulated to be
All experiments were performed in triplicate and the results due to the differentiated starches composition. TS contained more
were expressed as mean values standard deviation (SD). Tukeys amylose than WRS and this component leached out during gela-
test was used to determine significant (p < 0.05) differences tinization has the capacity to form a threedimensional network
between means. The effects of starch concentration or temperature stabilized by hydrogen bonds, consequently there is increase in vis-
and starch type (waxy rice starch, tapioca starch) as well as their cosity, whereas the ability of swollen starch granules composed
interactions on the values of measured parameters were analyzed mainly of amylopectin to form network is generally weak (Lu
by a two-way analysis of variance (ANOVA). Correlation coeffi- et al., 2009; Wang, Li, Wang, & zkan, 2010). The time-dependent
cients were determined using Pearsons correlation. Statistical rheological studies were performed to determine structural
analyses were carried out using Statistica 8.0 software (StatSoft changes due to the shear, i.e. destruction of the internal structure
Inc., USA). during flow. These experiments involved measurements of hystere-
sis loops and shear stress decays to calculate relative hysteresis
3. Results and discussion areas (Ar) and A, B parameters of Weltman equation (R2 > 0.994),
accordingly. The results found at 20 C are demonstrated in
3.1. Microstructure Fig. 2C and D. Considering F-values of ANOVA the Ar, A and B values
were predominantly affected by starch type (ST): Ar [F(1,16)
The microstructures of the white sauces were examined in rela- = 293.9, p < 0.001]; A [F(1,16) = 894.2, p < 0.001] and B [F(1,16)
tion to starch type (ST) and starch concentration (SC) and the = 913.7, p < 0.001]. Irrespectively of the applied ST, the Ar, A and B
images of WSs containing 2.0 and 3.5 wt% waxy rice starch magnitudes were positively (in majority r > 0.941) correlated with
(WRS) or tapioca starch (TS) were selected as representative of increasing starch concentration. Similar trends regarding evolution
studied systems (Fig. 1AD). Irrespectively, of the applied ST with of Ar with raising thickener concentration reported Bayarri and
increasing SC the white sauces (WSs) demonstrated rapid evolu- Costell (2011). Moreover, comparing adequate samples the values
tion of the formation of highly packed three-dimensional network, of Ar, A and B were in majority (p < 0.05) greater in TS- than WRS-
composed of milk proteins (mainly caseins) and starch particles. based sauces. The magnitudes of Ar and B are embodied with the
However, it was also found that WSs prepared with TS demon- extent of the destruction of sauces structure (Razavi, Taghizadeh,
strated more structured systems (Fig. 1C and D) than those made & Ardekani, 2010; Sharoba, El-Desouky, & Mahmoud, 2012). There-
with WRS (Fig. 1A and B). The oil droplets were generally distorted fore it may be assumed, that WSs made with TS (Fig. 1C and D)
from their typical spherical shape, moreover in samples containing needed more energy to destroy the structure responsible for flow
34 G. Bortnowska et al. / Food Chemistry 202 (2016) 3139

A B

C D

Fig. 1. Scanning electron micrographs of white sauces prepared with: 2.0 wt% waxy rice starch WRS (A), 3.5 wt% WRS (B) and 2.0 wt% tapioca starch TS (C), 3.5 wt% TS (D).
White arrows in A and B show RS2 particles.

time dependence than their counterparts (Fig. 1A and B) prepared followed an Arrhenius type model (R2 > 0.984) and the obtained
with WRS (Trrega & Costell, 2006). The temperature dependence from this equation magnitudes of activation energy (Ea) and Arrhe-
was studied in the range of 2080 C in relation to ST and starch con- nius constant (k0) are presented in Fig. 3. Results from ANOVA fol-
centration (SC). The flow curves were well (R2 > 0.992) described by lowed by the evaluation of F-values indicated, that starch
the HerschelBulkley (HB) equation and the derived rheological concentration in higher extent than starch type affected Ea values
parameters: r0, k and n are presented in Table 1. According to the [F(3,16) = 356.9, p < 0.001]. For both studied sets of sauces the val-
ANOVA, predominant effects of temperature on: k [F(3,16) = 971.4, ues of Ea decreased with raising SC and opposite effects were found
p < 0.001] and n [F(3,16) = 34.7, p < 0.001] parameters were found concerning k0 magnitudes. Similar trends were observed in other
in relation to WSs composed of 2.0 wt% starch (WRS, TS), whereas systems formulated with increasing thickener content (Hosseini-
regarding r0 [F(3,16) = 238.6, p < 0.001] in those prepared with Parvar et al., 2010). The detected results may be generally inter-
3.5 wt% starch. Moreover, irrespectively of the applied ST, with preted in terms that the higher the Ea values the greater the effect
the increase of temperature, the r0 and k magnitudes showed of temperature on the viscosity (Bortnowska, Krzeminska, &
descending tendency and opposite effects were found regarding n Mojka, 2013).
parameter (Table 1). These findings concerning effects of tempera- The frequency (x) dependence of G0 , G00 moduli of white sauces
ture on the rheological properties of liquid systems are in accor- (WSs) at 20 C is reported in Fig. 4A and B. In both studied sets of
dance with those reported by other authors (Augusto, Cristianini, samples, the G0 and G00 demonstrated ascending tendency with
& Ibarz, 2012; Hosseini-Parvar et al., 2010) and may be interpreted increasing x, indicating a viscoelastic structure of the sauces. On
in terms that with increase of temperature the Brownian motion is the other hand, irrespectively of the applied ST, raising starch
increased leading to the decrease in intermolecular interactions concentration yielded higher values of G0 and G00 , however the
between particles, consequently the fluid is becoming less pseudo- differences between these parameters were notably greater in
plastic and more Newtonian (Massa, Gonzlez, Maestro, Labanda, & TS- than WRS-based sauces (Fig. 4A and B). This may be explained
Ibarz, 2010; Xie et al., 2009). The values of consistency coefficient (k) by the fact that amylopectin fraction softens the structured
G. Bortnowska et al. / Food Chemistry 202 (2016) 3139 35

100 100
A B

Shear stress (Pa)


Shear stress (Pa)
10 10

1 1
0.1 10 1000 0.1 10 1000
Shear rate (s-1) Shear rate (s-1)

20 100 10
C D e f
e b d
c
16 80 0
a a b h
d
c
c c g
12

B (Pa s -1)
60 -10
Ar (%)

A (Pa)

a a
b
8 40 -20
d
f
c
4 20 e -30
b
a

0 0 -40
2 2.5 3 3.5 2 2.5 3 3.5
Starch concentration (wt%) Starch concentration (wt%)

Fig. 2. Flow curves of the white sauces made with waxy rice starch WRS 2.0 wt% WRS, 2.5 wt% WRS, 3.0 wt% WRS, 3.5 wt% WRS (A) or tapioca starch TS d 2.0 wt
% TS, r 2.5 wt% TS, N 3.0 wt% TS, j 3.5 wt% TS (B), relative thixotropic areas Ar% WRS, TS (C) and parameters of Weltman model: A columns and B lines
WRS, WRS, TS, TS (D). Mean values, within the same characteristics, marked with no common letters are significantly different (p < 0.05).

Table 1
Effect of temperature on white sauces rheological parameters (r0, k and n) derived from HerschelBulkley (HB) model in relation to starch type and concentration.

Starch (wt%) HB model WRS-based sauces TS-based sauces


Temperature (C)
20 40 60 80 20 40 60 80
2.0 r0 (Pa) 0.14 0.01c 0.21 0.02e 0.14 0.01c 0.03 0.00a 0.17 0.01d 0.20 0.01e 0.11 0.01b 0.11 0.01b
2.5 0.28 0.02e 0.24 0.02 cd 0.14 0.01b 0.08 0.01a 0.36 0.03f 0.29 0.02e 0.26 0.02de 0.23 0.01c
3.0 0.25 0.02bc 0.27 0.02c 0.23 0.02b 0.11 0.01a 0.84 0.06e 0.35 0.03d 0.35 0.02d 0.21 0.02b
3.5 0.89 0.06e 0.50 0.04d 0.46 0.04d 0.16 0.01a 1.47 0.09 g 0.95 0.06f 0.37 0.03c 0.27 0.02b
2.0 k (Pa sn) 2.15 0.19 g 0.86 0.07e 0.36 0.02b 0.17 0.01a 3.42 0.24 h 1.48 0.09f 0.76 0.06d 0.43 0.02c
2.5 2.97 0.21f 1.42 0.06d 0.81 0.05b 0.44 0.03a 5.49 0.32 g 3.05 0.17f 1.71 0.13e 1.05 0.05c
3.0 4.74 0.27e 2.57 0.19c 1.77 0.09b 1.15 0.07a 11.8 0.48 g 6.95 0.39f 4.65 0.28e 3.15 0.18d
3.5 7.53 0.41e 5.41 0.32c 3.15 0.27b 2.39 0.11a 19.7 0.79 h 14.1 0.51 g 9.39 0.42f 6.82 0.37d
2.0 n () 0.32 0.01a 0.36 0.02b 0.47 0.03d 0.49 0.03d 0.34 0.01ab 0.33 0.02a 0.43 0.02c 0.46 0.03 cd
2.5 0.29 0.01a 0.33 0.02b 0.34 0.03b 0.35 0.03bc 0.30 0.02a 0.31 0.02ab 0.38 0.03c 0.43 0.03d
3.0 0.27 0.02a 0.30 0.02ab 0.33 0.02c 0.34 0.01 cd 0.29 0.01a 0.31 0.03bc 0.34 0.02 cd 0.37 0.02d
3.5 0.24 0.01a 0.27 0.01b 0.32 0.02c 0.34 0.02c 0.27 0.01b 0.25 0.02a 0.26 0.02ab 0.31 0.02c

For the definition of abbreviations, see Section 2. Within the rows, values followed by different letters are significantly different (p < 0.05).

behaviour, giving rise to lower values of G0 modulus compared to may be assumed that, greater amylose/amylopectin ratio in TS
those which can be observed in systems composed of starches with than WRS most probably contributed to the more rapid increase
rich amylose content (Karaman, Yilmaz, & Kayacier, 2013). Thus it of elastic properties of TS- than WRS-based sauces (Fig. 1AD). Loss
36 G. Bortnowska et al. / Food Chemistry 202 (2016) 3139

100 400 starch type on tan d magnitudes was also confirmed by F-values
c of the ANOVA [F(1,16) = 318.3, p < 0.001]. The found results may
300 suggest that overall structure of sauces made with WRS was
80 weaker and less gellike than those prepared with TS (Fig. 1A
200 D). The G0 , G00 and G moduli were fitted to the power model
(R2 > 0.986) and the related magnitudes of: K0 , K00 , A, n0 , n00 and z

k0 x 104 (Pa sn)


Ea (kJ mol-1)

60 b are displayed in Table 2. ANOVA demonstrated that starch concen-


b 100
tration more than starch type affected the values of: K0 [F(3,16)
a a
0
= 514.1, p < 0.001], K00 [F(3,16) = 498.3, p < 0.001] and A [F(3,16)
40 a a a = 593.7, p < 0.001]. The corresponding samples, demonstrated in
a
b
c majority higher values (p < 0.05) of K0 in TS- than WRS-based
d -100
e e sauces and generally opposite effects were found regarding K00
20 f f
parameter. This might have resulted from differences in the inter-
-200
molecular forces, induced by changes in WSs composition (Arici
et al., 2014). Moreover, higher values of n00 than those in related
0 -300
samples regarding n0 may suggest evolution of the viscous behavior
2.0 2.5 3.0 3.5 of WSs with increasing x (Augusto, Ibarz, & Cristianini, 2013). The
Starch concentration (wt%) Bohlins parameters were calculated according to the theory that
emulsions can be modeled as a network of rheological units, which
Fig. 3. Activation energy (Ea columns) and Arrhenius constant (k0 lines) of white
interact for establishing system structure (Zaidel, Chronakis, &
sauces made with waxy rice starch (WRS) or tapioca starch (TS). Mean values, Meyer, 2013) and the obtained A and z values are featured in
within the same parameters, marked with no common letters are significantly Table 2. The z parameter is a measure of the number of rheological
different (p < 0.05). WRS, WRS, TS, TS. units correlated with one another in the three-dimensional struc-
ture, and the A one is related to the strength of the interactions
between these units (Bortnowska et al., 2014). The found results
tangent (tan d) was used to compare the ratios of loss modulus (G00 )
indicate that sauces prepared with 3.5 wt% TS yielded the highest
to storage modulus (G0 ) and determine whether elastic or viscous
values of z and A, suggesting the most complex structure
properties predominate in WSs. The tan d curves demonstrated
(Fig. 1AD) and probably the highest level of interactions between
ascending tendency throughout the tested frequency range (data
protein and starch coated droplets and three-dimensional network
not shown), reflecting the variations in interactive forces maintain-
formed by WSs components (Manoi & Rizvi, 2009). The A and z
ing the gel network (Liu & Tang, 2011). Moreover, it was noticed
magnitudes were well correlated (r > 0.932) with increasing starch
that in all samples the tan d values were lower than 1, however
concentration (SC). This may be interpreted that with greater
greater than 0.1 indicating that the WSs presented a structure that
starch content, both studied sets of sauces can longer keep original
was not a true gel (Dolz, Hernndez, & Delegido, 2006). The tan d
microstructure and exhibit stability towards phase separation
values at x of 1 Hz were taken in order to determine the changes
(Zaidel et al., 2013). Generalized CoxMerz rule (R2 > 0.979) was
occurring at different SC and thus compare samples (Table 2). It
found to be applicable to indicate shear/strain sensitivity of the
was observed, that tan d exhibited declining trend with increasing
WSs structures and the values of C and b constants are shown in
SC, implying evolution of the elastic (solid-like) properties of the
Table 2. The detected in majority greater than 1 values of C and b
WSs (Achayuthakan & Suphantharika, 2008). On the other hand,
parameters may be explained by the fact that network structure
comparing adequate samples, higher (p < 0.05) values of tan d were
of the sauces was less affected by dynamic oscillatory test than
found in WRS- than TS-based samples. The predominant effect of
steady shear experiment (Gamonpilas et al., 2011). The C values

1000 1000
A B

100 100
G',G" (Pa)

G',G" (Pa)

10 10

1 1
0.1 1 10 100 0.1 1 10 100
Frequency (Hz) Frequency (Hz)

Fig. 4. Frequency dependence of G0 and G00 moduli for white sauces made with waxy rice starch WRS G0 2.0 wt% WRS, s G00 2.0 wt% WRS; G0 2.5 wt% WRS, } G00 2.5 wt%
WRS; G0 3.0 wt% WRS, 4 G00 3.0 wt% WRS; G0 3.5 wt% WRS, h G00 3.5 wt% WRS (A) or tapioca starch TS d G0 2.0 wt% TS, s G00 2.0 wt% TS; r G0 2.5 wt% TS, } G00 2.5 wt% TS;
N G0 3.0 wt% TS, 4 G00 3.0 wt% TS; j G0 3.5 wt% TS; h G00 3.5 wt% TS (B).
G. Bortnowska et al. / Food Chemistry 202 (2016) 3139 37

Table 2
Tangent d (tan d), parameters of power law function describing: storage, loss and complex moduli (G0 = K0 xn , G00 = K00 xn and G = Ax1/z) and generalized CoxMerz rule
0 00

b
(g x Cfga c_  gxc_ ).

Parameters WRS-based sauces TS-based sauces


Starch concentration (wt%)
2.0 2.5 3.0 3.5 2.0 2.5 3.0 3.5
Tan d (at 1 Hz) 0.54 0.03f 0.49 0.02e 0.41 0.01d 0.33 0.02c 0.31 0.01c 0.18 0.01b 0.15 0.01ab 0.11 0.01a
0
K0 (Pa sn ) 5.62 0.29a 13.5 0.78c 26.8 1.02d 61.5 2.07 g 10.5 0.89b 32.1 0.14e 56.3 1.29f 149 3.72 h
n0 () 0.25 0.02e 0.20 0.01d 0.17 0.01 cd 0.12 0.01b 0.31 0.02f 0.16 0.01c 0.11 0.01b 0.06 0.00a
00
K00 (Pa sn ) 3.04 0.12a 6.67 0.47b 10.9 0.58d 20.3 1.13f 3.30 0.16a 5.86 0.34b 8.67 0.61c 17.2 0.96e
00
n () 0.32 0.02d 0.25 0.01c 0.21 0.01ab 0.18 0.01a 0.45 0.02f 0.37 0.01e 0.32 0.01d 0.23 0.01bc
A (Pa s1/z) 6.39 0.39a 15.1 0.98c 28.9 0.92d 64.8 1.14 g 11.1 0.87b 32.8 1.13e 57.2 1.87f 151 2.14 h
z () 3.66 0.12b 4.78 0.17c 5.64 0.26d 7.72 0.31e 3.06 0.14a 5.85 0.36d 8.43 0.52f 15.4 1.17 g
C () 2.68 0.13a 4.20 0.27c 4.88 0.29d 6.06 0.37e 3.12 0.13b 4.14 0.32c 2.64 0.06a 3.09 0.21b
b () 1.04 0.05a 1.07 0.04a 1.05 0.06a 1.11 0.08ab 0.98 0.07a 1.17 0.06bc 1.21 0.04 cd 1.27 0.08d

For the definition of abbreviations, see Section 2. Within the rows, values followed by different letters are significantly different (p < 0.05).

of WRS-based sauces and b ones of both types of sauces demon- of increasing lightness (data not shown) which is expected to have
strated ascending tendency with increasing SC, whereas no trends upward trend with the rise of particle concentration in colloidal
concerning C values were found regarding sauces prepared with TS. dispersions, because of greater degree of light scattering (Chung,
ANOVA revealed, that starch type was the factor that predomi- Degner, & McClements, 2013). The Ho is considered as qualitative
nantly affected changes of C [F(1,16) = 142.8, p < 0.001] and b [F attribute of color and is used to define the difference of a certain
(1,16) = 11.6, p < 0.01] parameters. The detected results may be color, whereas C is accounted as quantitative attribute of colorful-
interpreted that the greater are the values of C and b the greater ness and determines the degree of difference in Ho (Ma, Boye,
is ratio g/ga and bonding density between polymers, respectively Fortin, Simpson, & Prasher, 2013). Regarding studied WSs, the
(Augusto et al., 2012; Dolz et al., 2006). found results may implicate slightly changes in color from yellow
to green, simultaneously with decreasing vividness and may be
attributed to the differences in light absorption dependent on
3.3. Stability and color starch type and concentration (Guardeo et al., 2012;
McClements, 2002).
Centrifugation assay was used in order to monitor stability of
white sauces (WSs) towards phase separation and the values
expressed as stability index (SI) are listed in Table 3. In both exam- 3.4. Sensory evaluation
ined systems the magnitudes of SI demonstrated ascending ten-
dency with increasing starch concentration, besides as revealed The results of sensory analysis of white sauces (WSs) are pre-
ANOVA, this parameter mostly contributed [F(3,16) = 17.1, sented in Table 3. According to the ANOVA, starch concentration
p < 0.001] to the increase of WSs stability. It was found that, WSs (SC) had predominant effect on the: appearance [F(3,16) = 68.7,
with lower than 100% values of SI, exuded during centrifugation p < 0.001], texture [F(3,16) = 102.4, p < 0.001] and overall accept-
small amount of sedimented water phase, however without HAMS ability [F(3,16) = 60.5, p < 0.001], whereas flavor was mostly
granules (data not shown). This may suggest that they were partly affected by starch type [F(1,16) = 68.3, p < 0.001]. Regarding WRS-
embedded in the sauces network or adsorbed on the oil droplets based sauces, all studied attributes were positively correlated with
(Fig. 1A and B), thus increasing physical stability of the systems SC, however the differences between samples formulated with 3.0
due to formation of emulsions Pickering type (Protonotariou, and 3.5 wt% WRS were insignificant (p > 0.05). Whereas, in WSs pre-
Evageliou, Yanniotis, & Mandala, 2013). The investigated color pared with TS the correlations were generally very weak and in the
parameters (WI, Ho and C) are displayed in Table 3. ANOVA case of texture, flavor and overall acceptability negative, moreover
revealed that they were predominantly affected by starch concen- in majority insignificant (p > 0.05) variations were found between
tration (SC): WI [F(3,16) = 18.4, p < 0.001], C [F(3,16) = 74.8, samples made with 2.5 and 3.0 wt% starch. In both studied sets of
p < 0.001] and Ho [F(3,16) = 19.3, p < 0.001]. The WI and Ho showed samples, appearance was positively correlated with WI, Ho and
ascending tendency (r > 0.967) with raising SC and contrary effects negatively with C values obtained from instrumental analyses (data
were observed regarding C parameter. The increase in WI, found not shown). This may suggest that the panelists could not
in both examined sets of samples most probably was the result precisely determine colorfulness as it was possible using apparatus.

Table 3
Stability index (SI), color parameters (WI, Ho, C) and sensory attributes (appearance, texture, flavor, overall acceptability) of white sauces.

Parameters/attributes WRS-based sauces TS-based sauces


Starch concentration (wt%)
2.0 2.5 3.0 3.5 2.0 2.5 3.0 3.5
SI (%) 96.4 1.14a 98.7 1.37b 100 0.00c 100 0.00c 97.2 2.18ab 100 0.00c 100 0.00c 100 0.00c
WI 76.7 1.56a 79.8 1.84bc 80.9 1.72c 82.5 1.89d 78.9 3.16ab 81.2 3.09c 83.7 4.02de 85.2 3.14e
Ho 94.4 2.14a 95.1 1.93a 96.2 2.06b 98.4 2.19c 94.3 2.18a 95.6 2.87ab 98.1 2.16c 101 2.45d
C 16.9 0.92e 15.7 0.81d 14.8 0.53bc 13.6 0.49ab 17.2 0.91e 15.3 1.08 cd 13.5 0.82a 13.1 0.73a
Appearance 5.3 0.31a 6.1 0.39b 7.3 0.41d 7.2 0.29d 5.6 0.34a 7.2 0.53d 6.9 0.21 cd 6.3 0.49bc
Texture 4.9 0.32a 5.8 0.49b 8.4 0.73d 8.2 0.76d 6.1 0.54b 7.8 0.62c 7.7 0.68c 5.1 0.37a
Flavor 5.6 0.39bc 6,5 0.51e 6.6 0.48e 6.3 0.52de 5.8 0.39c 5.9 0.41 cd 5.4 0.23b 4.9 0.34a
Overall acceptability 5.2 0.48a 6.7 0.56c 7.8 0.74e 7.6 0.57de 5.7 0.46b 7.1 0.52 cd 6.9 0.49c 5.3 0.41ab

For the definition of abbreviations, see Section 2. Within the rows, values followed by different letters are significantly different (p < 0.05).
38 G. Bortnowska et al. / Food Chemistry 202 (2016) 3139

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