Physico-Chemical Gummi Confections
Physico-Chemical Gummi Confections
Physico-Chemical Gummi Confections
THESIS
Presented in Partial Fulfillment of the Requirements for the Degree Master of Science in
the Graduate School of The Ohio State University
By
Alexander Martin Siegwein
Graduate Program in Food Science and Nutrition
Copyright by
Alexander Martin Siegwein
2010
ABSTRACT
suppress the yield increase at each storage interval. The viscoelastic crossover frequency,
an indicator of viscoelastic stability, was also found to decrease as soy protein
concentration increased and to have a lower rate of increase during storage.
Additionally, water-dependent interactions were characterized as they relate to
soy concentration and storage time. Thermogravimetric analysis results indicated that the
primary water population was more easily removed in high-soy protein formulations.
Additionally, as storage time increased, soy protein maintained relative homogeneity of
the primary water population and removal of water required lower temperatures with the
soy formulation, indicating less entrapment of water throughout the storage period
studied.
Results from differential scanning calorimetry did not indicate a significant shift
in the glass transition temperature as soy concentration increased, most likely due to the
low concentration of plasticizing water. Neither gummi system exhibited distinct
endotherms associated with starch melting regardless of treatment; soy protein inclusion
did not prevent complete starch gelatinization during the confection process, as evidenced
by the lack of the typical starch melting endotherm. However, over time, the addition of
soy protein was able to prevent an increase in the T g of the gummi confections, perhaps
by interfering with starch re-association and retrogradation.
The changes in monomeric anthocyanin quantity, expressed as units of cyanidin
3-glucoside, which occurred as a result of confection processing were also analyzed using
ultraviolet spectroscopy. The soy gummi confections yielded higher anthocyanin
recovery compared to the standard formulation. This is probably due to the greater heat
iii
dissipation caused by a lower cooking viscosity from the soy formulation during the
confection process. Sensory analysis, conducted using a hedonic scale of acceptability,
showed that addition of soy protein improved acceptance for both texture and flavor. The
mechanism of improvement is thought to be related to the decreased rigidity (shortness)
of the product which augments mouth-feel and possibly flavor release.
All results indicate that soy protein has potential as a processing aide in gelled
confections by modulating physical properties. Gummi gel rheology was shown to be
dependent on soy concentration and storage time. Texture became less firm with
increasing soy protein concentration, and soy protein was shown to decrease firming over
time. The physical results support those of sensory analysis, in which it was found that
soy protein improved acceptability of the gummi confections for both texture and flavor.
The distribution of water and its dynamics were also shown to be time and concentration
dependent. Finally, addition of soy protein may aide in the processing stability of
anthocyanins by increasing heat dissipation.
iv
DEDICATION
ACKNOWLEDGEMENTS
vi
VITA
FIELDS OF STUDY
vii
TABLE OF CONTENTS
ABSTRACT ................................................................................................................... ii
DEDICATION ................................................................................................................v
ACKNOWLEDGEMENTS ........................................................................................... vi
VITA ............................................................................................................................ vii
FIELDS OF STUDY .................................................................................................... vii
TABLE OF CONTENTS............................................................................................. viii
LIST OF TABLES ....................................................................................................... xii
LIST OF FIGURES ..................................................................................................... xiii
1. INTRODUCTION .......................................................................................................1
2. STATEMENT OF PROBLEM ....................................................................................4
3. LITERATURE REVIEW ............................................................................................6
3.1
Gummi Confections...........................................................................................6
3.2
3.3
3.4
viii
3.5
4. METHODOLOGY .................................................................................................... 23
4.1
4.2
4.3
4.4
4.5
4.6
4.7
Abstract ........................................................................................................... 29
5.2
Introduction ..................................................................................................... 30
5.3
Methodology ................................................................................................... 32
5.3.1.
5.3.2.
5.3.3.
5.3.4.
5.3.5
5.3.6.
5.4
5.4.1
5.4.2
5.4.3
5.4.4
5.4.5
5.5
Conclusions ..................................................................................................... 54
6. EFFECTS OF SOY PROTEIN ON THE STORAGE STABILITY OF STARCHBASED GELLED CONFECTIONS ........................................................................... 56
6.1
Abstract ........................................................................................................... 56
6.2
Introduction ..................................................................................................... 56
6.3
Methodology ................................................................................................... 59
6.3.1
6.3.2
6.3.3
6.3.4
6.3.5.
6.4.
6.4.1
6.4.2
Effects of soy protein on the dynamic rheological properties over time ..... 70
6.4.3
6.5
Conclusions ..................................................................................................... 79
7. CONCLUSIONS ....................................................................................................... 80
Future Work............................................................................................................... 82
APPENDIX A ............................................................................................................... 83
APPENDIX B ............................................................................................................... 84
APPENDIX C ............................................................................................................... 85
REFERENCES .............................................................................................................. 86
xi
LIST OF TABLES
Table 1
Table 2
Table 3
Mean hedonic scores for Standard and 50% SPI gummi confections. ........... 51
Table 4
xii
LIST OF FIGURES
Figure 1
Figure 2
Figure 3
Figure 4
Example of the yield stress (seen as the onset point of decay) of a material
being subjected to an increasing oscillatory stress sweep. ............................. 20
Figure 5
Figure 6
Figure 7
Figure 8
Figure 9
Yield stresses (Pa) as a function of soy protein isolate (SPI) substitution. ..... 43
xiii
Figure 10
Figure 11
Figure 12
Figure 13
Monomeric anthocyanins content, expressed as units of cyanidin-3glucoside, in the gummi confections versus raw and boiled grape juice
concentrate. .............................................................................................. 53
Figure 14
Figure 15
Figure 16
Figure 17
Change in yield stress (Pa) as a function of time for both the Standard and
50% SPI treatments. ................................................................................. 71
Figure 18
Figure 19
Changes in the derivative weight loss curve of the Standard (19a, no soy)
and 50% SPI (19b) gummi confections. .................................................... 75
Figure 20
Comparison in the Tg onset temperature between the Standard and 50% SPI
gummi confections after 20 days. ............................................................. 78
xiv
CHAPTER 1
INTRODUCTION
in foods is as a texture modifier (Lusas & Riaz, 1995). Depending on the polysaccharide
gel system, soy protein has been shown to have variable results, enhancing (Baeza et al,
2002) or disrupting the gel's structural integrity (Ryan & Brewer, 2005). Addition of soy
protein ingredients to confections was suggested to improve handling properties and
stickiness (Rhee, 1994). Therefore, in gelled starch-sugar confections, a relatively model
gel system, soy proteins would perhaps be beneficial. Therefore, our hypothesis was that
soy protein affects the texture of the starch-based confections on a concentrationdependent basis. It is also hypothesized that soy protein will have a lasting effect on the
texture and related properties of starch-based confections throughout the defined storage
period.
To understand the textural changes that were affected upon addition of soy
protein, the rheological behavior was assessed. Oscillatory stress sweeps (OSS) reveal
the viscoelastic properties and behaviors of foods. Soy protein has been shown to have a
pronounced effect on viscoelasticity in gel and food systems (Ryan & Brewer, 2005;
Vittadini & Vodovotz, 2003). Oscillating frequency sweeps (OFS) were used to
characterize the rheological properties of the confections as a function of time. In these
gelled systems, OFS can reveal long-term stability (Rao, 2007), such as tendencies for
phase separation, retrogradation, syneresis, or sedimentation. If the addition of soy
protein creates a systemic instability, the oscillatory stress and frequency sweeps should
reveal differences between the various concentration treatments and time intervals.
In addition to the solid components of the gummi confection, water is another
critical component that affects the overall physical properties. Traditional methods of
describing water behavior (water activity, moisture content, and solvent retention
capacity) do not adequately describe the distribution and mobility of water in food
systems (Slade et al., 1991). Thermogravimetric analysis (TGA) can be used to
characterize the changes in physico-chemical properties of a food system as a function of
temperature. TGA can be used to track rate of moisture loss and differentiate different
water populations within a multi-component food (Fessas and Schiraldi, 2000).
Therefore, TGA will be used to characterize and compare water populations in the
gummi confection system and how those are affected by addition of soy protein isolate.
The aim of this investigation was to assess the effect of soy protein addition on
the physico-chemical properties of a starch confection system. Specifically, the textural,
thermal, and rheological properties of starch-based grape juice confections will be
evaluated upon incorporation of multiple levels of soy protein. The effect of soy protein
on monomeric anthocyanin stability, such as cyanidin-3-glucoside (see Appendix A),
which is known to be compromised in high-temperature food preparation methods (Patras
et al., 2010; Edwards, 2000), will also be assessed in the gummi confections. The
sensory acceptability of gummi confections made with soy protein will be evaluated by
an untrained panel with particular emphasis on texture and flavor. Lastly, the storage
stability of gummi confections formulated with and without soy protein will be assessed
through 10 and 20 days using thermal and rheological characterizations.
CHAPTER 2
STATEMENT OF PROBLEM
Soy protein concentration and storage time will modulate the physico-
Aim 1: To characterize and compare the thermal and rheological properties of starchbased gummies with multiple levels of soy protein incorporation.
Aim 2: To characterize the changes that occur in gummi candies with and without soy
protein during storage.
Aim 3: To determine how soy protein addition affects the sensory acceptability and
processing stability of anthocyanins using UV spectroscopy.
CHAPTER 3
LITERATURE REVIEW
3.1
Gummi Confections
In 2009, non-chocolate chewy confectionery sales increased by 11.2% (Anon,
2010). Chewy sugar-based candies are a stable part of the American confectionery
industry (Young, 1998) with sales of over $1.6 billion (Anon, 2010). However, the soft
candy sector of the sugar confectionery industry had recently suffered losses to
production and value (USCB 2005) that industry professionals have attributed to lack of
innovative products (Anon, 2006b). Development of a highly acceptable soy-containing
gummi confection may represent a key new niche for this industry and a passageway into
the area of functional foods.
3.2
food augmentation (Green et al., 2006; Sethi et al., 2007; Prasad, 2009; Serventi et al.,
2009) that is becoming more and more accepted by Americans (Nelson, 2008). However,
it also has great potential as a functional ingredient, imparting unique physical properties
when incorporated into the formulation (Vittadini & Vodovotz, 2003; Lusaz & Riaz,
1995). Soy protein has also been implicated improving product stability, such as
impeding product staling (Vittadini & Vodovotz, 2003; Anhong et al., 2006) and freeze6
et al., 2009). The choice of gelling agent can have the biggest impact on final product
quality and attributes, and therefore must receive special attention. Gelatin, the
traditional gelling agent used in gummy formulations, is losing favor due to cultural,
dietary, and safety concerns (Lennox, 2002; McHugh, 2003), as well as the desire for
unique textural properties (Poppe, 1995). Specialty starches have been developed to meet
the demand for gelatin-free candies while providing unique sensory and physical
properties (Warnecke, 1991). Starch-set gummies, the largest volume gum/jelly product
in the United States (Warnecke, 1991), have greater acid and heat stability and have
much shorter gelation time than gelatin gummies (Burg, 1998), thereby conferring
functional and pecuniary advantages. The most commonly used starches for gummi and
7
soft jelly applications are acid-thinned because they have relatively low hot viscosity
(Ellis et al., 1998; Singh et al., 2007) and can therefore be agitated and pumped with
minimum energy expenditure. Wheat starches have received renewed attention due to
their unique properties (Sloan, 2006). Gummies are traditionally made in a batch process
(Scuderi, 2002; Burey et al., 2009) which, although not modern, does prevent mechanical
damage upon the swollen starch granule (Zallie, 2006). In a standard starch-based soft
candy, a thin boiling starch is heated in water beyond the gelatinization temperature,
mixed with a corn syrup sucrose solution, and boiled down to the desired soluble solids
content. In contrast to relatively well-understood gelatin gummi formulations, the
interactions that occur between water and starch in a high sugar environment (>65%,
such as in gummy-like confections) have not been studied adequately. Chang et al.,
(2002) demonstrated that certain sugars can, in fact, plasticize starch and reduce firmness,
but at lower concentrations. Kasapsis et al., (2004) showed that high sugar
concentrations reduce the structural order of a model confection system, as opposed to
gelatin which is reinforced by high sugar (Kasapsis et al., 2003).
Composite or mixed gels are becoming more common in foods due to the desire
for unique texture and handling characteristics (DeMars & Ziegler, 2001; Burey et al.,
2009). However, the interactions (or lacks thereof) that create such a novel system are
less well understood. In protein-polysaccharide systems, the level of interaction or
separation depends on many factors, such as system pH, moisture, material history, as
well as polymer properties such as charge, size, and morphology (Burey et al., 2009).
For gelled confectionery systems, which are held together by a continuous network
whose dynamics are retarded by high solutes, an added protein may create a
environment, like confections, as they pertain to product stability have not been
investigated. Gel-formation capacity and viscosity of soy protein hydrates is related to
soy protein composition (native vs. denatured and the extent of denaturation),
9
temperature, and pH (Arrese et al., 1991). Ideally, soy protein and starch will each
contribute to gel formation and firmness. However, soy protein isolate (SPI) may affect
sugar recrystallization, glass transitions, starch retrogradation, and other physical effects
of soft jelly candy as observed in other food systems (Vittadini et al., 2003; Luo et al.,
2003; Tsai et al., 1998). Therefore, to understand how SPI affects the thermal and
physical properties of starch-based soft jelly confections, it is important to first
characterize the physico-chemical properties of the model system without SPI
incorporation.
A basic soft jelly and gummy formulation is a heterogeneous mixture of water,
sugars, and gel-forming polymers. In such a system, water acts as a plasticizer and
lowers the glass transition temperature (Tg) of food constituents. Fructose has also
demonstrated high plasticization capacity on the amylopectin fraction of starch (Liu et al.,
2004). In boiled sweets, like gummy candies and toffees in which final water content is
low (<20%), the product is in an amorphous rubber (preferable) or an amorphous glass,
depending on the extent and rate of water removal (Roos et al., 1991). The addition of
polymeric compounds, such as starch and protein, to a sugar solution tends to increase the
Tg (Rogers et al., 2006), slowing crystallization of amorphous sugars due to decrease free
volume, molecular mobility, and diffusivity (Roos et al., 1996).
Changes in water mobility, independent of moisture content, may be caused by
continuous chemical interactions in the system, such as recrystallization, starch
retrogradation, and glassy/rubbery equilibrium (Cornillon et al., 2000) affecting, among
other things, the shelf life of the product. For example, recrystallization of amorphous
sugars due to increased molecular mobility is an undesirable defect in soft, gummy-like
10
11
12
Figure 1
Typical DSC thermogram of a gummi confection made with wheat starch. The
highlighted area is a putative glass transition.
13
14
Fessas and Schiraldi (2001) have described the use of TGA in bakery products to
monitor the rate of water release as a function of temperature, assigning ingredient effects
to the different components of the food. This means that water is not uniformly
partitioned within foods. Water that is less strongly associated with food components is
removed at lower temperatures by a simple diffusion mechanism (Fessas & Schiraldi,
2001), whereas strongly associated water is removed at high temperatures by a change in
the physical properties of the system itself. Therefore, using TGA will characterize the
water distribution of a standard starch-based soft jelly candy and the changes arising from
the addition of SPI to the candy formulation.
15
Figure 2
16
3.5
17
Figure 3
18
By definition, rheology is the study of deformation and flow (Rao, 1999), which
would therefore include texture analysis. However, the underlying viscoelastic properties
that manifest as textural changes can be probed by small-deformation rheological
analysis. Using a rheometer, it is possible to observe the viscoelastic behavior of a given
material as a function of applied stress and the rate thereof. Oscillatory rheometry is an
established technique for measuring flow and deformation of food matter under applied
stress or strain (Rao, 2007). Rheological properties are also likely to correlate strongly
with mouth-feel (Sukha et al., 2003). Oscillatory stress sweeps can reveal basic
relationships between a food's elastic and viscous behavior. When G' > G, the sample
behaves more like an elastic solid and has higher stress resistance (Brummer, 2005).
Yield stress, or the stress at which a material is strained beyond its linear viscoelastic
region (LVR) and begins to deform permanently (Rao, 2007), is indicative of a gel's
structural integrity. Figure 3.4 depicts the results of a typical yield stress analysis using
an oscillatory stress sweep.
19
Figure 3.4.
4
Example of the yield stress (seen as the onset point of decay) of a material being
subjected to an increasing oscillatory stress sweep.
20
In addition to stress sweeps, frequency sweeps can also reveal dependency on rate
of applied stress and how that relates to micro-structural stability (Pai & Khan, 2002). In
particular, the viscoelastic crossover (G'-G) cross-over frequency can be predictive of
long-term stability (Ross-Murphy, 1994) and any interactions which may affect it (Franco
et al., 1997). For example, a liquid food material displaying a frequency-independent
elastic modulus (G') with a steadily decreasing viscous modulus (G) at high frequencies
may be experiencing extensive polymeric interactions and behave more like a solid
(Ikeda & Nishinari, 2001; Sans et al., 2005), something with serious implications for an
industrial food manufacturer. Alternately, high frequencies can induce polymer
dissocation and cause a gel material to behave more like a liquid (Gigli et al., 2009).
Figure 3.5 depicts the cross-over frequency of a typical oscillatory frequency sweep
analysis on a viscoelastic gel (frequency dependency presents itself as changing slopes on
the log-log axes). Sivaramakrishnan et al., 2004, used an oscillatory frequency sweep to
characterize how an added hydrocolloid can disrupt the normal structural associations
within a model bread system and at what point the dominant structural component is the
added ingredient.
21
Figure 3.5.
5
22
CHAPTER 4
METHODOLOGY
4.1
ingredients were mixed by shaking prior to pouring into the kettle (30 qt., jacketed, plus
scraping mixer; Schweppe, Addison, IL 60101). Water and 65 oBrix concord grape juice
concentrate (Welch's Foods Inc., Concord, MA 01742) amounts were equivalent across
all variables. Acid-thinned wheat starch (Gemstar 1090, Manildra Group USA, Shawnee
Mission, KS 66205) and soy protein isolate (Prolisse, Cargill, Inc., Minnetonka, MN
55391) were added to the juice-water solution and then heated to cooking temperature,
which was was set to and maintained at 100 oC. Confections were subsequently cooked
to a final soluble solids content of 70 oBrix (approximately 25 minutes), verified using a
high-solids refractometer (Fisher Scientific, Pittsburgh, PA 15275). Confections were
then set in Clean Set 0736 cornstarch (Cargill Inc., Cedar Rapids, IA 52406) and
cured/stoved for 24 hours at 38 oC in an Isotemp drying oven (200 series, model 215F,
Fisher Scientific, Pittsburgh, PA 15275). The final total solids content was
approximately 78-80 oBrix for all formulations, where 80 oBrix is considered standard for
gummi-type confections (Koh & Mulvaney, 2004). All equipment used in the gummi
batching process is shown in Figure 6. After curing, candies were cooled to room
temperature, gently brushed free of cornstarch, and then heat-sealed in polyethylene bags.
23
Samples were stored at room temperature (~ 20 oC) until analysis at day 1, 10, and 20
(note: concentration study used day 1 samples only). Samples were analyzed as-is,
without modification; outer skins were not removed for any analysis. The densities of all
samples was approximately 1.4 (mass/volume) and the pH values (Orion Research,
Beverly, MA) were between 3.20 and 4.30 (Table 01).
Formulation
Standard
33% SPI
50% SPI
66% SPI
Table 1
68 oB
Concord
Grape
Juice (%)
69.9
69.9
69.9
69.9
H20
(%)
19.1
19.1
19.1
19.1
Acid-thinned
soy protein
wheat starch
isolate
(%)
(%)
pH
11
0
3.2
7.3
3.7
4.1
5.5
5.5
4.2
3.7
7.3
4.3
*Shaded rows only used for storage time study
24
Figure 6
25
4.2
the confections. Three separate batches were tested in quadruplicate for each
formulation. Samples, removed centrally from the interior of the confections were
weighed to 10 15 mg and loaded into platinum TGA pans. A high-resolution
thermogravimetric analyzer (Model Q5000, TA Instruments, New Castle, DE) was used
for all TGA experiments. Nitrogen was used as the purge gas and set to flow rates of 10
and 25 ml/min for the balance and sample pans, respectively. Samples were heated from
~30 oC to 220 oC using a high resolution (Hi-Res) ramp of 20 oC/min resolved to 3
o
C/min whenever the instrument detects a change in weight. Samples were analyzed for
both %weight loss and derivative weight loss (%/oC). Derivative weight loss (dTGA)
describes the rate of weight loss (%) as a function of temperature (Fessas & Schiraldi,
2001) with peaks indicating temperature ranges of accelerated weight loss. Assuming
that all weight loss up to 175 oC is attributed to moisture loss (Fessas & Schiraldi, 2001),
the moisture content (MC) was calculated using equation 1.
Eq. 1
M.C. = initial mass (g) final mass (g)
initial mass (g)
4.3
x 100
an Instron 5542 Universal Testing Machine operating with Bluehill software. For the
concentration study, samples were analyzed in quadruplicate for each of three batches for
the standard (0% soy), 33%, and 50% soy gummies. The 66% soy protein gummies
26
could not be evaluated because the samples were destroyed by the texture profiling
method. For the storage time study, samples were analyzed in quadruplicate for each of
three batches for the standard (0% soy) and 50% SPI samples. Two-step, 50%
compression at a rate of 2 mm/sec was performed to simulate mastication (Daubert &
Foegeding, 2003). Gumminess, a function of cohesiveness and hardness (Bourne, 2002)
was used as one of the traits of comparison between samples and, according to
Szczesniak (1962), is the energy required to disintegrate a semisolid food, through
mastication, to a point where it can be swallowed.
4.4
Rheological Analysis
All sample analyses were performed using a stress-controlled AR2000ex
rheometer (TA Instruments, New Castle, DE). Samples were cut with a circular die to a
flat cylindrical shape and then compressed to a thickness of 2 mm with the 20 mm plate
geometry. Oscillatory experiments for stress, frequency, and time were performed to
elucidate rheological characteristics. Oscillatory stress sweeps (OSS) were performed
first at with a range of 0.10 to 4,000 Pa at 1 Hz to determine the linear viscoelastic region
(LVR). The critical (yield) stress, the stress at which the materials deformation was no
longer elastic (Liehr, 2000) was obtained. Oscillatory frequency sweeps (OFS) were also
performed to determine the linear response range at a stress chosen from within the linear
region of the OSS. To determine temperature-dependent behavior, samples were
deformed at 1 Hz and constant stress (from the LVR) and heated from room temperature
to 100 oC. Lastly, oscillatory time sweeps and creep tests were performed under linear
conditions to determine time-dependent behavior. Oscillatory time sweeps (OTS) were
used to determine pre-shear requirements for other oscillatory sweeps regarding testing
27
within the LVR. Results (data not shown) did not indicate any reproducible pre-shear
requirements for other rheometric tests.
4.5
UV-Spec Analysis
The Standard and the 50% SPI treatments were analyzed and compared at day 1
Sensory Analysis
An untrained hedonic sensory panel consisting of students and faculty recruited at
the Parker Food Science building was conducted to determine the acceptability of fresh
gummi confections made with and without soy protein isolate (50% SPI level only).
Panelists (n = 40) were asked to score texture and taste on a scale from 1 to 10 (10 = like
extremely, 1 = dislike extremely). A sample questionnaire and the participatory letter can
be found in Appendices B & C, respectively.
4.7
Statistical Analysis
Data were analyzed using one-way ANOVA with Tukey's multiple comparison
method (p = 0.05) in Minitab 15. Data that failed a test for normality were tested with
the Kruskal-Wallis one-way ANOVA test of median equality using SPSS 18.
28
CHAPTER 5
5.1
Abstract
The effects of increasing soy protein concentration on the physico-chemical
properties of starch confectionery gels were investigated using thermal and rheological
analyses. Texture analysis revealed that soy protein decreases hardness and
cohesiveness, but with a more dramatic effect on the latter, perhaps demonstrating
potential as a texture modifier. Rheological analysis determined that increasing soy
protein concentration progressively decreased the elastic properties of the starch network,
both by decreasing yield stress and the viscoelastic crossover frequency. High levels of
soy protein also created a more homogeneous water population, one which is lost at
lower temperatures than standard starch gummi confections. Sensory analysis revealed
an improvement in flavor and texture acceptability of gummi confections upon addition
of soy protein. Finally, monomeric anthocyanin recovery was greater in gummi
confections prepared with soy protein, perhaps by improving heat dissipation during
processing.
29
5.2
Introduction
Gelled confections and candies, collectively referred to as gummies (Edwards,
2000), are a large, stable, and growing business (Young, 1998); As of 2006, industry
experts have reported as high as 8.4% growth in the gummi candy sector, mostly
attributed to innovative formulations (Anon, 2006). Many of the most common and
recognizable gummi confections are typically made with gelatin as the active agent of
gelation (Lennox 2002). However, gelatin is not the only option for creating gummi-type
candies. Starches may be preferred for being free of animal by-products and the
associated concerns (Lennox 2002). However, starch-based confections are sometimes
described as short an undesirable texture attribute characterized by a firm, brittle gel
(Burg, 1998).
Texture is a primary determinant of quality in gelled confectionery products and,
due to their relatively simple composition, provide an ideal model for mixed gel
investigations (DeMars & Ziegler, 2001). Gumminess and chewiness are texture analysis
descriptors that are particularly applicable to gelled confections (Borwankar, 1992).
Firmer (short) gummies that are more prone to fracture during mastication are often
described as chewy, while softer gummies that dissolve during mastication are described
as gummy (DeMars & Ziegler, 2001). Shortness is a texture defect associated with
decreased sensory acceptability of gelled confections (Burg, 1998), so quantifying the
firmness (shortness) of the gummi confections as it relates to sensory acceptability is
prudent. One of the primary uses of soy protein in foods is as a texture modifier (Lusas
& Riaz, 1995). Depending on the polysaccharide gel system, soy protein has been shown
to have variable results, enhancing (Baeza et al, 2002) or disrupting the gel's structural
30
integrity (Ryan & Brewer, 2005). Addition of soy protein ingredients to confections was
suggested to improve handling properties and stickiness (Rhee, 1994). In a gelled starchsugar confections, a relatively model gel system, soy proteins would perhaps be
beneficial. Therefore, our hypothesis was that soy protein affects the texture of the
starch-based confections on a concentration-dependent basis.
To understand the textural changes that were affected upon addition of soy
protein, the rheological behavior was assessed. Oscillatory stress sweeps (OSS) reveal
the viscoelastic properties and behaviors of foods. Soy protein has been shown to have a
pronounced effect on viscoelasticity in gel and food systems (Ryan & Brewer, 2005;
Vittadini & Vodovotz, 2003). Oscillating frequency sweeps (OFS) were used to
characterize the rheological properties of the confections as a function of time. In these
gelled systems, OFS can reveal long-term stability (Rao, 2007), such as tendencies for
phase separation, retrogradation, syneresis, or sedimentation. If the addition of soy
protein creates a systemic instability, the oscillatory stress and frequency sweeps should
reveal differences between the various concentration treatments.
In addition to the solid components of the gummi confection, water is another
critical component that affects the overall physical properties. Traditional methods of
describing water behavior (water activity, moisture content, and solvent retention
capacity) do not adequately describe the distribution and mobility of water in food
systems (Slade et al., 1991). Thermogravimetric analysis (TGA) can be used to
characterize the changes in physico-chemical properties of a food system as a function of
temperature. TGA can be used to track rate of moisture loss and differentiate different
water populations within a multi-component food (Fessas and Schiraldi, 2000).
31
Therefore, TGA will be used to characterize and compare water populations in the
gummi confection system and how those are affected by addition of soy protein isolate.
The aim of this investigation was to assess the effect of soy protein addition on
the physico-chemical properties of a starch confection system. Specifically, the textural,
thermal, and rheological properties of starch-based grape juice confections will be
evaluated upon incorporation of multiple levels of soy protein. The effect of soy protein
on the anthocyanin stability, which is known to be compromised in high-temperature
food preparation methods (Patras et al., 2010; Edwards, 2000), will also be assessed in
the gummi confections.
5.3
Methodology
Confections were prepared using the ingredients listed in Table 02 as follows: all
ingredients were mixed by shaking prior to pouring into the kettle (30 qt., jacketed, plus
scraping mixer; Schweppe, Addison, IL 60101). Water and 65 oBrix concord grape juice
concentrate (Welch's Foods Inc., Concord, MA 01742) amounts were equivalent across
all variables. Acid-thinned wheat starch (Gemstar 1090, Manildra Group USA, Shawnee
Mission, KS 66205) and soy protein isolate (Prolisse, Cargill, Inc., Minnetonka, MN
55391) were added to the juice-water solution and then heated to cooking temperature,
which was was set to and maintained at 100 oC. Confections were subsequently cooked
to a final soluble solids content of 70 oBrix (approximately 25 minutes), verified using a
high-solids refractometer (Fisher Scientific, Pittsburgh, PA 15275). Confections were
then set in Clean Set 0736 cornstarch (Cargill Inc., Cedar Rapids, IA 52406) and
cured/stoved for 24 hours at 38 oC in an Isotemp drying oven (200 series, model 215F,
Fisher Scientific, Pittsburgh, PA 15275). The final total solids content was
32
approximately 78-80 oBrix for all formulations, where 80 oBrix is considered standard for
gummi-type confections (Koh & Mulvaney, 2004). After curing, candies were cooled to
room temperature, gently brushed free of cornstarch, and then heat-sealed in polyethylene
bags. Outer skins were not removed for any analysis. The densities of all samples was
approximately 1.4 (mass/volume) and the pH values (Orion Research, Beverly, MA)
were between 3.20 and 4.30 (Table 01).
68 oB
Concord
Acid-thinned soy protein
Grape
H20
wheat starch
isolate
Formulation
Juice (%)
(%)
(%)
(%)
pH
69.9
19.1
11
0
3.2
Standard
69.9
19.1
7.3
3.7
4.1
33% SPI
69.9
19.1
5.5
5.5
4.2
50% SPI
69.9
19.1
3.7
7.3
4.3
66% SPI
Table 2
Formulations for gummi confections used in the concentration study.
33
C/min whenever the instrument detects a change in weight. Samples were analyzed for
both %weight loss and derivative weight loss (%/oC). Derivative weight loss (dTGA)
describes the rate of weight loss (%) as a function of temperature (Fessas & Schiraldi,
2001) with peaks indicating temperature ranges of accelerated weight loss. Assuming
that all weight loss up to 175 oC is attributed to moisture loss (Fessas & Schiraldi, 2001),
the moisture content (MC) was calculated using equation 1.
Eq. 1
M.C. = initial mass (g) final mass (g)
initial mass (g)
x 100
the samples were destroyed by the texture profiling method. Two-step, 50% compression
at a rate of 2 mm/sec was performed to simulate mastication (Daubert & Foegeding,
2003). Gumminess, a function of cohesiveness and hardness (Bourne, 2002) was used as
one of the traits of comparison between samples and, according to Szczesniak (1962), is
the energy required to disintegrate a semisolid food, through mastication, to a point
where it can be swallowed.
5.3.3. Rheological Analysis
All sample analyses were performed using a stress-controlled AR2000ex
rheometer (TA Instruments, New Castle, DE). Samples were cut with a circular die to a
flat cylindrical shape and then compressed to a thickness of 2 mm with the 20 mm plate
geometry. Oscillatory experiments for stress, frequency, and time were performed to
elucidate rheological characteristics. Oscillatory stress sweeps (OSS) were performed
first at with a range of 0.10 to 4,000 Pa at 1 Hz to determine the linear viscoelastic region
(LVR). The critical (yield) stress, the stress at which the materials deformation was no
longer elastic (Liehr, 2000) was obtained. Oscillatory frequency sweeps (OFS) were also
performed to determine the linear response range at a stress chosen from within the linear
region of the OSS. To determine temperature-dependent behavior, samples were
deformed at 1 Hz and constant stress (from the LVR) and heated from room temperature
to 100 oC. Lastly, oscillatory time sweeps and creep tests were performed under linear
conditions to determine time-dependent behavior. Oscillatory time sweeps (OTS) were
used to determine pre-shear requirements for other oscillatory sweeps regarding testing
within the LVR. Results (data not shown) did not indicate any reproducible pre-shear
requirements for other rheometric tests.
35
was used (Figure 7, differing letters above error bars designate statistical significance, p <
0.05). The results indicate that while the lower concentration of soy protein has a great
impact on hardness, the internal structure is most compromised at higher soy protein
concentrations. These results suggest that soy protein can modulate shortness of texture
in gelled confections without sacrificing the structural integrity of the system. A similar
progressive decrease in hardness was observed by Limroongreungrat and Huang (2007)
in pasta upon addition of soy protein. The decrease in hardness could have resulted from
direct disruption of the starch network or, as has been shown in bread systems, the
hydrated soy protein may have acted as a macro-molecular plasticizer and thereby
lowering starch-network stiffness (Vittadini & Vodovotz, 2003). It is important to note
that hardness in gelled confections can be misrepresented by case hardening, a surface
phenomenon caused by moisture loss that manifests as a skin(Ziegler et al., 2003), that
is not necessarily representative of the total physical nature of the sample. However, case
hardening only became more noticeable as soy protein increased and did not mask the
overall softening effect.
37
Figure 7
38
39
Figure 8
40
This also seems to indicate that soy protein is compromising the rigid starch
network rather than forming a gel. Gelation of soy protein isolate is largely dependent on
concentration, pH, ionic strength, temperature, and time (Renkema, 2001). This gummi
system was low pH (3.2 for the control and 4.1 to 4.3 for the soy protein treatments), low
ionic strength (no added salts),relatively low soy protein isolate concentration (3.75% to
7.25%), and prepared at high temperature over a short time period during which water is
progressively evaporated. It is suggested that, in this confection system, there is
insufficient time and too many interfering solutes for soy protein gelation to occur.
Therefore, the soy protein isolate used in this investigation acts as a non-gelling
ingredient, meaning there is no interaction between protein units in such a way that a
three-dimensional structure is formed (Hermansson, 1985). The extent of denaturation is
also not known. Prolisse SPI is made in such a way that there should be minimal protein
denaturation; however, DSC analysis of ingredients revealed no endotherms associated
with SPI denaturation (data not shown). Gelation of denatured soy protein under gummi
manufacturing conditions would require a bridging cation, commonly calcium, more
time at high temperatures, and/or a higher concentration of soy protein (Wagner et al.,
1995) or at least a lower concentration of soluble solutes (Renkam, 2001, Gu et al.,
2009). It is also possible that soy protein may not be able to form a continuous gel
because the confectionery system's pH is near the isoelectric point (4.5) of this soy
protein (Hermannson, 1986; Srejic, 2006; Gennadios et al, 1993). Because soy protein's
impact on a carbohydrate gel's physical properties have been shown to be heavily
impacted by system pH (Ipsen, 1995), this effect is most pronounced at the 66%
41
concentration. The pH should not have affected the starch network itself (Russell &
Oliver, 1989).
Soy protein may alternatively impede starch hydration during confection
preparation and has been observed in other food systems (Ribotta et al., 2005; Molina et
al., 1976) due to soy's strong affinity for water (Yao et al., 2006). However, DSC
analysis revealed no endothermic peaks that would represent starch crystal melting (data
not shown). Alternately or in parallel, the soy protein may simply have interfered with
starch gelation. This is supported by the decreasing hardness values observed in Figure
8. Hua et al., (2004) demonstrated that soy protein can indeed inhibit continuous
formation of a hydrocolloid network in a carbohydrate system.
42
Figure 9
43
Figure 10
44
45
crossover frequency may be due to a destabilizing effect of soy protein, suggesting that,
by causing the G-G crossover to occur at lower frequencies, soy protein was
compromising the starch network (responsible for the elastic properties) of the gel. The
greatest changes to the system stability occurred at the 33% and 66%, the latter being the
sample which was so destabilized by the high soy protein substitution that it could not be
analyzed with the texture analyzer.
46
Figure 11
47
C (Aseeva et al., 2009). This is based on the known final total solids (consistently 78-
80%) and the observation that samples removed from the TGA oven at 150 oC were
browned, dry, and brittle while samples tested through to 200 oC were ash. This
temperature range of 150 to 200 oC corresponds to the second dTGA peak observed in all
samples. Weight lost at lower temperatures (less than 100 oC), assumed to be water
removed by simple diffusion (Fessas & Schiraldi, 2001) was low, 3 6%, with very high
sample-to-sample variability. However, it is still possible to differentiate the variables
based on the primary water population, in which the rate of weight loss is greatest from
approximately 100 to 150 oC. Figure 12 shows that this population of water is relatively
uniform except for the 66% SPI treatment, in which the peak terminates at a lower
temperature. Zhang (2004) observed that, upon adding soy protein to bread, the
derivative weight loss peak shifted to lower temperatures, indicating that the soy system
had a weaker water association. Prolisse SPI is considered to be highly soluble (Ohr,
2006; Adams, 2007), but it would seem that its capacity to hold water at high
temperatures is low relative to the other components of the gummi system (starch,
monosaccharides). Because it still has some ability to hold water, it must not have been
rendered fully denatured by the high temperature (100 oC) gummi process (Elmore et al.,
2007; Hermannson, 1986). In the confection system, the differences in peak
temperatures are only significantly different (p < 0.05) at the highest level, 66%, of soy
protein substitution. This indicates that, above 50% SPI, the network in the confection
48
began to lose its ability to bind water, rather than an incremental decrease as soy protein
increased.
49
Figure 12
Peak termination temperatures of derivative weight loss curves of gummi candies with
increasing levels of soy substitutions. Inset graph depicts typical dTGA weight loss peak for
66% SPI variable versus Standard control.
50
n = 40
Standard
50% SPI
Table 3
Code
Texture
Flavor
a
115
7.56
7.30a
698
5.05b
6.23b
*Different letters indicate significant differences (p < 0.05)
Mean hedonic scores for Standard and 50% SPI gummi confections.
51
52
Figure 13
53
5.5
Conclusions
The results of this investigation have demonstrated that addition of soy protein
54
55
CHAPTER 6
6.1
Abstract
The effects of soy protein addition on the storage stability of starch-based gummi
confections were investigated using thermal and rheological analytical techniques. Soy
protein addition improved the textural stability of the gummy confection by maintaining
lower cohesiveness and decreases the confection's resistance to stress. During storage,
soy gummi confections demonstrated altered water dynamics, as evidenced by a lower T g
and lower loss temperatures suggesting the potential of using soy protein isolate as a
functional ingredient for improved textural profile during storage.
6.2
Introduction
Gelled confections and candies, collectively referred to as gummies (Edwards,
2000), are a large, stable, and growing business (Young, 1998); As of 2006, industry
experts have reported as high as 8.4% growth in the gummi candy sector, mostly
attributed to innovative formulations (Anon, 2006). Many of the most common and
recognizable gummi confections are typically made with gelatin as the active agent of
gelation (Lennox 2002). However, gelatin is not the only option for creating gummi-type
candies. Starches may be preferred for being free of animal by-products and the
associated concerns (Lennox 2002). However, starch-based confections are sometimes
described as short an undesirable texture attribute characterized by a firm, brittle gel
56
(Burg, 1998). Furthermore, starch gels have a tendency to retrograde which can manifest
as further increase in gel firmness or shortness (Leon et al., 1997) which may lower
consumer acceptance.
Texture is a primary determinant of quality in gelled confectionery products and,
due to their relatively simple composition, provide an ideal model for structure-function
investigations (DeMars & Ziegler, 2001). Gumminess and chewiness are texture
analysis descriptors that are particularly applicable to gelled confections (Borwankar,
1992). Firmer (short) gummies that are more prone to fracture during mastication are
often described as chewy, and softer gummies that dissolve during mastication are
described as gummy (DeMars & Ziegler, 2001). One of the many uses of soy protein in
foods is as a texture modifier (Lusas & Riaz, 1995). Depending on the polysaccharide
gel system, soy protein has been shown to have variable results, enhancing (Baeza et al,
2002) or disrupting the gel's structural integrity (Ryan & Brewer, 2005). Addition of soy
protein ingredients to confections was suggested to improve handling properties and
stickiness (Rhee, 1994). In gelled starch-sugar confections, a relatively model gel
system, soy proteins would perhaps be beneficial to long-term storage stability. In a
previous study (Siegwein, 2010), increasing levels of soy protein added to gummi
confections were shown to modulate firmness and increase water mobility using
rheological and thermal analytical techniques, respectively. Therefore, our hypothesis
was that soy protein has a lasting effect on the texture of starch-based confections
throughout the defined storage period.
To understand the textural properties that were affected upon addition of soy
protein, the viscoelastic behavior obtained through oscillatory stress sweeps (OSS) can be
57
assessed. Soy protein has been shown to have a pronounced effect on viscoelasticity in
gel and food systems (Ryan & Brewer, 2005; Vittadini & Vodovotz, 2003). Analysis of
long-term stability of gelled systems utilizing oscillating frequency sweeps (OFS)
revealed tendencies for phase separation, retrogradation, syneresis, or sedimentation
(Rao, 2007), If the addition of soy protein creates a systemic instability, the oscillatory
stress and frequency sweeps should reveal differences in the dynamic rheological
properties between the time intervals.
Water is another critical component that affects the overall physical properties of
gummy confections. Traditional methods of describing water behavior (water activity,
moisture content, and solvent retention capacity) do not adequately describe the
distribution and mobility of water in food systems (Slade et al., 1991), particularly in
regards to long-term stability (Sablani et al., 2007) and, therefore, quality. Thermal
analytical techniques, including differential scanning calorimetry (DSC) and
thermogravimetric analysis (TGA) can be used to characterize the changes in physicochemical properties of a food system as a function of temperature. DSC can be used to
quantify 2nd order transitions, such as the glassy-rubbery transition, which is associated
with an increase in molecular motion of the amorphous phase of materials as they change
from the glassy (rigid) to the rubbery (flexible) state (Slade et al., 1991). This state
change is driven by plasticizing water (Roos & Karel, 1991), meaning the water itself
must be characterized.
The aim of this investigation was to determine how soy protein affects storage
stability of gummi confections. Specifically, the textural, thermal, and rheological
properties of starch-based grape juice confections will be evaluated at 1, 10, and 20 days.
58
6.3
Methodology
Confections were prepared using the ingredients listed in Table 02 as follows: all
ingredients were mixed by shaking prior to pouring into the kettle (30 qt., jacketed, plus
scraping mixer; Schweppe, Addison, IL 60101). Water and 65 oBrix concord grape juice
concentrate (Welch's Foods Inc., Concord, MA 01742) amounts were equivalent across
both treatments. Acid-thinned wheat starch (Gemstar 1090, Manildra Group USA,
Shawnee Mission, KS 66205) and soy protein isolate (Prolisse, Cargill, Inc.,
Minnetonka, MN 55391) were added to the juice-water solution and then heated to
cooking temperature, which was was set to and maintained at 100 oC. Confections were
subsequently cooked to a final soluble solids content of 70 oBrix (approximately 25
minutes), verified using a high-solids refractometer (Fisher Scientific, Pittsburgh, PA
15275). Confections were then set in Clean Set 0736 cornstarch (Cargill Inc., Cedar
Rapids, IA 52406) and cured/stoved for 24 hours at 38 oC in an Isotemp drying oven
(200 series, model 215F, Fisher Scientific, Pittsburgh, PA 15275). The final total solids
content was approximately 78-80 oBrix for all formulations, where 80 oBrix is considered
standard for gummi-type confections (Koh & Mulvaney, 2004). After curing, candies
were cooled to room temperature, gently brushed free of cornstarch, and then heat-sealed
in polyethylene bags. Samples were stored at room temperature (~ 20 oC) until analysis
at day 1 (fresh), 10, and 20. Samples were analyzed as-is, without modification; outer
skins were not removed for any analysis. The densities of all samples was approximately
1.4 (mass/volume) and the pH values (Orion Research, Beverly, MA) were between 3.20
and 4.30 (Table 01).
59
68 oB
Concord
Acid-thinned
soy protein
Grape
H20
wheat starch
isolate
Formulation
Juice (%)
(%)
(%)
(%)
pH
69.9
19.1
11
0
3.2
Standard
69.9
19.1
5.5
5.5
4.2
50% SPI
Table 4
Formulations for gummi confections used in storage time study.
60
x 100
62
63
6.4.
64
Figure 14
65
Hardness results are presented in Figure 15. There was no change in hardness
over 20 days for the standard. Hardness increased significantly (p < 0.05) in 50% SPI
samples at each storage interval studied. For each interval, all samples were significantly
(p < 0.05) different from each other. During storage, the 50% SPI treatment was
observed to have developed a tough skin, possibly due to case hardening caused by
surface dehydration of the water associated with soy protein. Soy protein has high water
affinity (Vittadini & Vodovotz, 2003), but may be easily removed depending on the food
matrix (Smith, 2003). A previous study (Siegwein, 2010) also showed that soy protein
could cause the gummi system to more readily lose moisture, although the distribution
across the sample was not investigated. Phase separations are common in composite gels
(Burey et al., 2009) and may be evidenced by the increased hardness observed in Figure
TPA2.
66
Figure 15
67
68
Figure 16
69
6.4.2 Effects of soy protein on the dynamic rheological properties over time
Significant differences between standard and 50% SPI samples at all storage
intervals were observed with the standard exhibiting a much greater stress resistance,
manifesting as a higher yield stress value (Figure 17). The standard samples increased
significantly in yield stress at each storage interval, while, in the 50% SPI samples, the
yield stress increased significantly only at the 20 day interval. Higher yield stress values
are indicative of a system that is progressively becoming more resistant to permanent
deformation and perhaps more glassy than rubbery (Ollett et al., 1991), and the relative
magnitudes of increasing yield stresses, approximately 1000% vs. 100% for the Standard
and the 50% SPI, respectively, reveal that the 50% SPI is much more resistant to the
formation of a highly elastic (rigid or short) than the Standard.
70
Figure 17
Change in yield stress (Pa) as a function of time for both the Standard and 50%
SPI treatments.
71
72
Figure 18
73
74
Figure 19
Changes in the derivative weight loss curve of the Standard (19a, no soy) and 50% SPI (19b) gummi
confections.
75
storage suggesting a shift of the standard towards a less rubbery (more elastic or solidlike) state at room temperature. The lack of any melting endotherms in the ~60 C range
indicates that there is either no detectable crystalline starch (full gelatinization) typical of
freshly made starch-based gummi confections (Burey et al., 2009) or that there is not
enough plasticizing water to facilitate the reaction (Zeleznak & Hoseney, 1987).
77
Figure 20
78
6.5
Conclusions
The results of this investigation have demonstrated that addition of soy protein
79
CHAPTER 7
CONCLUSION
It was hypothesized that adding soy protein to a gummi confection system would
have a profound impact on its physico-chemical properties, both as a factor of soy protein
concentration and storage time, due to interactions between the main system components
(water, sugars, starches, and proteins). To that end, the following aims were addressed.
Aim 1: To characterize and compare the thermal and rheological properties of
starch-based gummies with multiple levels of soy protein incorporation.
Addition of soy protein isolate was found to dramatically alter the physicochemical properties of gummi-type confections. Soy protein seems to affect an overall
softening of gummy candies, most likely due to partitioning the water populations away
from, and possibly directly disrupting, the starch gel network. This softening effect,
which manifested as decreased hardness, yield stress, and elasticity, became more
pronounced as soy protein concentration increased. At higher concentrations, soy protein
may completely disrupt the starch network, and may even replace starch as the
continuous phase or render the whole system discontinuous (no ordered associations),
creating a weak gel held together more by hydrophobic interactions and overall solids
concentration. The softening of the gel network due to the inclusion of soy protein could
potentially be used as a processing aide to modulate a specific textural defect, shortness,
associated with starch-gelled sugar confections. Increasing soy concentration also caused
80
81
shortness, which is in agreement with the texture and rheology results, yielding a
smoother texture and enhanced flavor perception.
UV Spectroscopy
Despite the disruptive effects that soy protein appears to have on the macrostructural properties of gummi confection, it has demonstrated potential as a processing
aide that improved nutritive pigment (color) stability. Monomeric anthocyanin recovery
was significantly improved (30% more), in the soy gummi formulation. The mechanism
is thought to be based on the effect of viscosity on heat capacity. Addition of soy protein
noticeably decreased cooking viscosity, allowing for greater dissipation of heat.
Future Work
Characterizing the effects of soy protein addition on gummi confections has
yielded a preliminary understanding of how soy protein behaves in a high-solids starch
gel and how that changes over time. As a seminal investigation, there is still much
research needed to fully understand the molecular nature of the interactions and
underlying dynamics that occur upon creation of a mixed/composite gel by addition of
soy protein to a high sugar starch network. Specifically, how soy proteins degree of
denaturation and comprising subunits affect physical properties. The possible thermoprotectant action of soy protein on juice anthoycanins during the preparation gummi
confections deserves more attention as a potential delivery system. Lastly, it may be
worthwhile to map the drivers of sensory acceptability for gummi confections to
determine how best to apply texture modifiers like soy protein isolate.
82
APPENDIX A
83
APPENDIX B
84
APPENDIX C
85
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