Food Chemistry 263 (2018) 292–299

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

Pulp and Jam of Gabiroba (Campomanesia xanthocarpa Berg): T

Characterization and Rheological Properties
Shayla Fernanda Barbieria, Carmen Lúcia de Oliveira Petkowicza,
Rossana Catie Bueno de Godoyb, Henriette Cordeiro Monteiro de Azeredoc,
⁎
Célia Regina Cavichiolo Francod, Joana Léa Meira Silveiraa,
a
Biochemistry and Molecular Biology Department, Federal University of Paraná, 81.531-980 Curitiba, PR, Brazil
b
Brazilian Agricultural Research Corporation, Embrapa Forestry, 83.411-000 Colombo, PR, Brazil
c
Brazilian Agricultural Research Corporation, Embrapa Tropical Agroindustry, 60.020-181 Fortaleza, CE, Brazil
d
Cell Biology Department, Federal University of Paraná, 81531-980 Curitiba, PR, Brazil

A R T I C LE I N FO A B S T R A C T

Keywords: This study evaluated the physicochemical characterization and rheological behavior of gabiroba pulp, and a
Gabiroba pulp gabiroba jam formulation. Gabiroba pulp presented a heterogeneous ultrastructure with a denser area formed by
Gabiroba jam a compact mesh and a porous interface containing fibers. The fibers’ presence promoted a slip effect when the
Rheology gabiroba pulp was subjected to shear. Gabiroba pulp showed a gel behavior with thermal stability. Gabiroba jam,
Physicochemical characterization
developed using pulp as the raw material, had shear thinning behavior exhibiting yield stress described by the
Herschel-Bulkley model. The dynamic oscillatory analysis showed that gabiroba jam typically behaved like a gel,
i.e., G′ values higher than the G″ in all frequency ranges evaluated. The results showed that gabiroba pulp is
suitable for use as a raw material in the development of food products such as jam, encouraging the preservation
of this native Brazilian species.

1. Introduction Garbelotti, 2008; Andrade, Helm, Mazza, & Mazza, 2012; Santos et al.,
2012; Embrapa, 2015; Barbieri et al., 2017). The nutritional properties
The commercialization of native fruit plays an important role in of gabiroba pulp make the pulp suitable to consume in natura and as a
social perspectives in countries around the world, including Brazil raw material with excellent properties for application in beverage, ice
(Clerici & Carvalho-Silva, 2011). Brazil is the third-largest producer of cream, and jam industries (Lisbôa, Kinupp, & Barros, 2011). However,
fruit worldwide with about 45 million tons per year, of which 65% is despite the potential application, gabiroba pulp is not used commer-
consumed internally and 35% is destined for the foreign market cially.
(Abrafrutas, 2017). Fruit pulps have been increasingly used as raw material for the
Among the diversity of native fruit, numerous species from the production of food and cosmetic products (Kowalska, Czajkowska,
Myrtaceae family (Barroso, 1978), 145 genera and 5970 known species, Cichowska, & Lenart, 2017). Thus, the knowledge of rheological
are spread across the world (The plant list – Myrtaceae, 2013). One of properties is essential for the design of processing equipment, product
them is the Campomanesia xanthocarpa Berg, popularly known as ga- development, quality control and consumer acceptability (Ahmed,
biroba, a Brazilian native species that is investigated in the present Ramaswamy, & Hiremayh, 2005).
study. The rheological properties of pulps from different fruits, such as:
Gabiroba fruit is composed of 7% calyx, 16% seeds, 17% peel, and mango (Mangifera indica) (Ahmed et al., 2005), araçá (Psidium cat-
60% pulp (Santos, Correia, Petkowicz, & Cândido, 2012). The fruits can tleianum sabine) (Haminiuk, Sierakowski, Vidal, & Masson, 2006), ja-
be considered a functional food due to nutritional properties as high buticaba (Myrciaria cauliflora) (Sato & Cunha, 2007), siriguela (Spondias
contents of carbohydrates (7.8–10.2%), dietary fiber (4.1–9.8%), pro- purpurea L.) (Augusto, Cristianini, & Ibarz, 2012), guava (Psidium gua-
tein (1.0–1.1%), and lipids (0.7–1.9%). In addition, the fruits have a java) (De Oliveira, Rossi, & De Barros, 2011) and pequi (Caryocar cor-
large amount of water (79.1–83.5%), vitamin C (826.26 mg g−1) and iaceum) (Sousa, Queiroz, Fiqueiredo, & Lemos, 2014) have been in-
total phenolics (19.59 µg g−1) (Vallilo, Moreno, Oliveira, Lamardo, & vestigated. In most of the studies, the influence of temperature on the

⁎
Corresponding author.
E-mail address: jlms12@ufpr.br (J.L.M. Silveira).

https://doi.org/10.1016/j.foodchem.2018.05.004
Received 26 October 2017; Received in revised form 27 April 2018; Accepted 1 May 2018
Available online 02 May 2018
0308-8146/ © 2018 Elsevier Ltd. All rights reserved.
S.F. Barbieri et al. Food Chemistry 263 (2018) 292–299

rheological behavior was analyzed through steady-state shear experi- 2.2.2. Sedimentation and moisture analysis
ments. It was observed that the viscosity of the pulps decrease with the In the sedimentation test, the undiluted gabiroba pulp and five
increase of temperature and they showed shear-thinning behavior. water-diluted samples, at pulp:water ratios (w/w) of 1:1, 1:5, 1:10,
Regarding the gabiroba pulp, to date, only two studies were found 1:20, and 1:30, were analyzed. The gabiroba pulp was firstly thawed
characterizing its rheological behavior at steady-state shear conditions. and then diluted in ultrapure water – 18 Ω (Master system-MS2000,
De Oliveira et al. (2011) and Santos et al. (2012) showed the shear- Gehaka, São Paulo, Brazil) at the five proportions cited above. Each
thinning behavior of the gabiroba pulp was described by the empirical diluted sample was homogenized for 10 s in a vortex (Model AV-2,
rheological models of Ostwald Waale, Herschel-Bulkley, and the Power Gehaka, Sâo Paulo, Brazil). The sedimentation process, at 25 °C, was
Law. However, no information was found on the viscoelastic properties followed through photographs (without flash) for 186 h until stable
of gabiroba pulp. sedimentation was reached, taking one photo every 30 min using a
Fruits, especially those with less shelf-stability in natura and rich in timer coupled to the camera (Canon 60 D with lens 24-105 mm F/4.0).
bioactive compounds, like gabiroba, can be preserved in the form of The sedimentation analysis of the photographs was done through the
jam. Products like jam and jellies make the fruits available for con- ImageJ program, version 1.50 c (Java 1.7.0-45).
sumption during off-season (Abid, Yaich, Hidouri, Attia, & Ayadi, 2018; A moisture analyzer (Model MB25, OHAUS®, Shanghai, China) was
Shinwari & Rao, 2018). Jam is a food prepared by boiling fruit pulp used to evaluate the total solid content of the pulp.
with sucrose, pectin, acid, and other ingredients (preservative, coloring,
and flavoring materials) and is consumed widely in the world (Baker, 2.2.3. Jam cook-concentration process
Berry, Hui, & Barrett, 2005). The components present in the jam for- Gabiroba jam was prepared with the required amounts of fresh pulp
mulations are the main factors that affect their rheological properties, and sucrose mixed in an open pan, heated up to the boiling point, and
which have been studied for jams of mango (Basu & Shivhare, 2010), concentrated by evaporation until the desired concentration of soluble
peach (Falguera, Mengual, Vicente, & Ibarz, 2010), apple (Garrido, solids content of 67.5° Brix, as measured with a digital refractometer
Lozano, & Genovese, 2015), blueberry (Zhang et al., 2016) and tomato (Model ABBE-WAY-2S, Atago®, Tokyo, Japan). The required amount of
(Belović, Torbica, Pajić-Lijaković, & Mastilović, 2017). commercial pectin was separately dissolved in water with part of the
Thus, in the present study it was developed a jam as a sustainable sucrose and allowed to hydrate under stirring for 24 h (Einhorn-Stoll,
way of using and consuming the gabiroba pulp. The rheological beha- 2018). The pectin dispersion was added to the pulp-sucrose mix to-
vior of a gabiroba jam was characterized for the first time in this work. wards the end of the concentration process. The citric acid was added
Considering the nutritional properties of gabiroba fruit and its potential just before the end of the process to keep the pH around 3.5, monitored
application in the development of food products, the rheological be- with a digital pH meter (Model DMPH-1, Digimed, São Paulo, Brazil).
havior, structural morphology, and physicochemical characteristics of Finally, each sample was hot-filled at about 90 °C into three sanitized
gabiroba pulp were also evaluated. and labelled glass jars, which were sealed with their screw tops and
stored for later measurements.

2. Materials and methods 2.2.4. Rheological analyses

The rheological measurements were carried out using a rheometer
2.1. Material Haake Mars II (Thermo Scientific, Karlsruhe, Germany) equipped with
three parallel plate geometries: one smooth (20 mm diameter, 1 mm
Ripe gabiroba (Campomanesia xanthocarpa Berg) fruits were col- gap) for jam analysis; one smooth (35 mm diameter, 1.0 mm gap) for
lected from a conservation area in Irati-Paraná/Brazil, located at the pulp analysis and another with a grooved surface (35 mm diameter,
geographic coordinates of 25° 25′ south latitude, 50° 36′ west longitude, 1.0 mm gap) for steady-state shear and freezing point analyzes of ga-
and 25° 17′ south latitude, 50° 30′ west longitude. The fruits were se- biroba pulp. The temperature was controlled by a circulating water
lected and washed, the peel and seeds were removed using a specific bath (DC5-Haake K15, Karlsruhe, Germany), regulated by a Peltier
device (Model DM-JI-05/SP1, Macanuda, Santa Catarina, Brazil), and device (Haake UTM Controller, Karlsruhe, Germany), and kept at 25 °C
the resulting pulp was frozen at −20 °C for further analyses. (except for the temperature sweep and freezing point analysis). The
Gabiroba jam was prepared using fresh pulp and sucrose (purchased experiments were carried out in triplicate with mean and standard
from a local market, Curitiba, Brazil) (1:1 w/w), citric acid (P.A-ACS, deviation evaluated by the statistical software Graphpad Prism 5. The
Sigma-Aldrich, Rio de Janeiro, Brazil) (0.2%), and commercial citrus samples were placed in the rheometer and kept for 5 min before ana-
pectin (GENU® – Rapid set, CPKelco, São Paulo, Brazil) (0.2%). lysis. A new sample was used for each repetition. The software used for
the evaluation of data was HAAKE RheoWin Sofware, version 4.3.

2.2. Methods 2.2.4.1. Steady-state shear measurements. The steady-state shear

experiments for gabiroba pulp were carried out in the shear rate (γ ̇)
2.2.1. Scanning electron microscopy (SEM) range of 0.001–100 s−1 for 300 s in CR mode (controlled shear rate) at
Gabiroba pulp was analyzed by scanning electron microscopy (SEM) 25 °C, using different annular gap sizes between the parallel plate
(Model VEGA3 LMU, Tescan, Kohoutovice, Czech Republic), equipped geometry with gaps of 1.0, 1.5, 2.0, and 2.5 mm in parallel plate
with a detector (SDD 80 mm2) and AZ Tech Advanced software. The geometries with grooved surfaces. The steady-state shear experiments
electron micrographs were obtained at a 15 kV accelerating voltage. for gabiroba jam were carried out in the shear rate range of
The gabiroba pulp was put on aluminum stubs with double-face tape 0.01–100 s−1 for 300 s in CR mode at 25 °C with an annular gap size
and dried at 25 °C. Then, it was submitted to metallic coating with gold of 1.0 mm, in parallel plate geometries with smooth surfaces.
for 2 min with thickness of 10 nm, under argon atmosphere, using The rheological behavior of the jam described by the flow curves
metallic coating equipment (Model SCD 030, Pfeiffer, Balzers, was fitted to the Herschel-Bulkley model. The Herschel-Bulkey model is
Liechtenstein). represented by the equation τ = τ0 + K (γ ̇) n , where τ is shear stress
The energy dispersive spectrometry analysis (EDS) was randomly (Pa), τ0 is yield stress (Pa), γ̇ is shear rate (s−1), K is the consistency
performed in the sample. X-ray detector coupled to SEM and under the coefficient (Pa.sn), and n is the flow behavior index (dimensionless) that
same SEM operating conditions was used to take the electron micro- signifies the extent of deviation from Newtonian behavior (Rao, 2007).
graphs. This procedure was carried out at the Electron Microscopy
Center at the Federal University of Paraná, Curitiba, Brazil. 2.2.4.2. Dynamic shear measurements. Oscillatory stress sweeps

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between 0.01 and 100 Pa were performed for gabiroba pulp at a for indication of how the gabiroba pulp is going to behave under pro-
frequency of 1.0 Hz and at 25 °C to determine the linear viscoelastic cessing conditions as well as in the rheological properties. Furthermore,
range. Then, frequency sweep measurements were carried out at 2.0 Pa, fiber content can also impart some functional properties to foods, e.g.,
a shear stress value within the linear viscoelastic range; the frequency increase water holding capacity, oil holding capacity, emulsification
sweeps were from 0.01 to 100 Hz. The gabiroba jam was analyzed by and/or gel formation (Elleuch et al., 2011; Belović, Torbica, Pajić-
frequency sweep (0.01–10 Hz) at 25 °C, at shear stress value of 1.0 Pa Lijaković, & Mastilović, 2017).
which was previously determined by oscillatory stress sweep between Therefore, in order to determine the elemental chemical composi-
0.01 and 100 Pa, 1 Hz, at 25 °C. tion of gabiroba fresh pulp, the energy dispersive spectrometry analysis
The temperature sweep was performed between 5 °C and 95 °C with (EDS analysis) by SEM was performed. This analysis showed that ga-
a heating rate of 1 °C min−1, a constant frequency (1 Hz), and constant biroba fruit mainly contained carbon (67%) and oxygen (30.8%), fol-
stress (2.0 Pa for pulp and 1.0 Pa for gabiroba jam). Next, a cooling step lowed by potassium (1.8%), phosphorus (0.2%), sulfur (0.1%), mag-
was performed using the same conditions as the heating experiment nesium (0.1%), and calcium (0.1%). The presence of carbon and oxygen
from 95 °C to 5 °C. The plate temperature was controlled by a Peltier as the major compounds is expected due to the amount of carbohy-
effect device. Silicone oil was applied around the exposed sample sur- drates in the gabiroba pulp (7.8–10.2% as dry pulp) (Santos et al., 2012;
face and a solvent trap was used to permit efficient temperature reg- Barbieri et al., 2017), notably pectins and hemicelluloses (galactoglu-
ulation and prevent water evaporation. comannans), as reported recently (Barbieri et al., 2017).
The freezing point of the gabiroba pulp was assessed by decreasing
the temperature from 25 °C to −10 °C and melting point temperature
3.2. Sedimentation analysis of gabiroba pulp
was assessed by increasing it from −10 °C to 25 °C at a rate of
0.5 °C min−1, constant frequency (1.0 Hz), and constant stress (2.0 Pa).
Fruit pulps are considered suspensions where solid particles are
The parallel plate geometry with grooved surface was used.
dispersed into an aqueous system (Sato & Cunha, 2009). The stability of
a suspension can be affected by the total solid content and it is very
3. Results and discussion important for process control as a quality parameter and in the choice
of application in a product (Servais, Jones, & Roberts, 2002).
3.1. Scanning electron microscopy (SEM) and energy-dispersive So, the total solid content of gabiroba pulp was determined
spectrometry analysis (EDS) of gabiroba pulp (17.7% ± 0.8) and the stability of pulp was evaluated in a sedi-
mentation process. The sedimentation of undiluted pulp and for five
The surface ultrastructure of gabiroba pulp was studied for the first pulp:water ratios (1:1, 1:5, 1:10, 1:20, and 1:30, w/w) are shown in
time with the use of SEM. We can observe in Fig. 1, in the scanning Fig. 2A and B.
electron micrographs, the panoramic images showing the mesh pattern, Undiluted pulp and pulp:water (1:1 ratio) samples remained stable
architecture and ultrastructure of the gabiroba pulp at the magnifica- with a single visible phase; pulp precipitation was not observed in any
tions of 150× (A), 300× (B, C), and 700× (D). In image (A), two of the samples during the sedimentation period evaluated (Fig. 2B). The
different ultrastructure patterns can be observed. A dense, irregular- stability of undiluted pulp and pulp:water (1:1 ratio) is due probably to
looking mesh formed by juxtaposed aggregates was present in the pulp the fiber content, as shown by the porous interface containing fibers
( ), and in the central portion of this mesh, larger and smaller diameter (insoluble portion) in the surface ultrastructure of gabiroba pulp ob-
perforations were observed, in which the fibers form a more open mesh tained by SEM analysis (Fig. 1). Fibers have swelling capacity and can
( ). Image (B) shows a more compact mesh, which presents a flatter, increase water retention, preventing syneresis and increasing the sta-
smooth, and regular face interposed with a structure forming ag- bility of the suspension (Elleuch et al., 2011). This sedimentation sta-
gregates, i.e., lumpy portions ( ). Images (C) and (D), in greater mag- bility of undiluted pulp and the 1:1 pulp:water concentration suggest
nitude, showed the lower-density area of this pulp, where it is possible that gabiroba pulp has potential for use in the preparation of con-
to observe the perforations as well as the pattern of the fibers that make centrated juices without the presence of additives. This feature is in-
up this mesh ( ). teresting since most fruit juices and nectars use some kind of additive to
These images show that the gabiroba pulp presents a heterogeneous increase viscosity, stabilization and prevention of pulp sedimentation
ultrastructure composed of two polymerization interfaces, a denser area (Coelho et al., 2017).
formed by a compact mesh (soluble portion) and a porous interface After 186 h of sedimentation, the other dilutions analyzed had se-
containing fiber (insoluble portion). The heterogeneous ultrastructure dimentation rates of 4%, 15%, and 13% for the 1:5, 1:20, and 1:30
with a porous interface containing fiber observed by SEM contributes pulp:water ratios, respectively. Interestingly, even for the gabiroba pulp

Fig. 1. Ultrastructural analysis in scanning electron microscopy (SEM) for the gabiroba pulp. The image (A) shows a panoramic image. The image (B) shows a greater
magnification of the denser area. The images (C) and (D) show the area of lower density with characteristic perforations and the presence of fibers. Image mag-
nifications: (A) 150×, (B) 300×, (C) 300×, and (D) 700×. This experiment was carried out in triplicate. The white arrows show: ( ) A dense mesh formed by
juxtaposed aggregates of irregular appearance. ( ) Perforations of larger and smaller diameters and the presence of fibers, characteristic of a more open, less dense
mesh. ( ) The polymerization pattern of the compact mesh with a flatter, smoother, and regular face. ( ) The polymerization area of lower density with char-
acteristic perforations and fibers.

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Fig. 2. Sedimentation analysis of gabiroba pulp during 186 h (A). Sedimentation of gabiroba pulp as a function of time. (B) Undiluted pulp (Pulp) and pulp:water
ratios (P:W) from 1:1 to 1:30, after sedimentation stability.

at the 1:30 pulp:water ratio, the sedimentation rate was only 13%; this
result may suggest the use of gabiroba pulp for nectar formulations.
Coelho et al. (2017), in their studies of passion fruit (Passiflora edulis)
nectar, showed similar results, i.e., sedimentation rates between 10%
and 15%; however, the authors proposed in the formulation of passion
fruit nectar the addition of polysaccharides (carrageenan or guar) as
thickening additives.

3.3. Steady-state shear properties of gabiroba pulp

According to the literature the fruit pulps rich in insoluble fibers,

can show different rheological behavior when compared to other fruit
pulps (Tonon, Alexandre, Hubinger, & Cunha, 2009). Usually, the flow
behavior of fruit pulps is strongly influenced by the amount of sus-
pended particles, which imparts a shear-thinning characteristic to the Fig. 3. Influence of shear rate on the viscosity curve of gabiroba pulp
pulps (Saravacos, 1970). The SEM analysis showed the presence as well (0.001–100 s−1) at 25 °C, in parallel plate geometries with grooved surfaces
as the pattern of the fibers of gabiroba pulp. Thus, the steady-state shear using different gaps (1.0–2.5 mm).
properties of gabiroba pulp were evaluated.
Fig. 3 demonstrates the viscosity curve of gabiroba pulp and the Cunha (2009) also demonstrated the apparent wall slip in their studies
dependence between the shear rate values and the annular gap size with açai pulp (Euterpe oleraceae Mart.), relating the wall slip to the
used. At 1 s−1, the apparent viscosity decreases from 828 Pa s to chemical composition of açai pulp (fibers, proteins, and lipids).
157 Pa s between the gap sizes of 1.0 and 2.5 mm, respectively. After Viscosity curves for gabiroba pulp were generated by evaluating
the measurements, the phase separation of insoluble particles within shear rates from 0.001 to 100 s−1 using geometry with grooved surfaces
the analyzed pulp sample was clearly visible. The insoluble particles led to avoid apparent wall slip. According to the literature, the serrations,
to a slip (apparent wall slip) between the sample and the surface of the when dipped into the bulk fluid, provide a good grip for the sample,
parallel plate from the rheometer. The slip behavior of the gabiroba eliminating or decreasing the occurrence of slip effects (Tonon et al.,
pulp sample may justify the differences in the viscosity analyses. 2009). However, for the gabiroba pulp, the slip effects occurred for both
In the literature, the slip phenomenon and its influence on the ap- the smooth (data not shown) and grooved geometries (Fig. 3). These
parent viscosity measurements was observed during the rheological results suggested that the apparent wall slip effect observed in steady-
measurements of particulate systems, such as foams, emulsions, sus- state shear measurements is related to the presence of the fibers that
pensions, gels, and polymer solutions (Barnes, 1995; Bertola, Bertrand, make up the gabiroba pulp.
Tabuteau, Bonn, & Coussot, 2003). Tonon, Alexandre, Hubinger, and

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Fig. 4. Dynamic rheology properties of gabiroba pulp. (A) Frequency sweep (0.01–100 Hz) at 25 °C, showing the frequency dependence of the elastic modulus (G′,
full symbols) and viscous modulus (G″, open symbols). (B) Elastic modulus (G′) and viscous modulus (G″) as a function of temperature for heating and cooling cycles
(5–95 °C) with a constant temperature rate of 1 °C min−1, at 1.0 Hz and 2.0 Pa, using the geometry with a smooth surface. (C) Freezing point dependence of the elastic
modules (G′). Temperature sweep at the 25 °C to −10 °C range (cooling and heating cycles) at 1.0 Hz, 2.0 Pa, at a constant temperature rate of 0.5 °C min−1 using the
geometry with a grooved surface.

Unlike most of the studies found in the literature on rheological the temperature sweep, the viscoelastic properties of the pulp subjected
behavior of fruit pulps, in the present study, the gabiroba pulp was not to the heating followed by cooling (5 °C–95 °C) were studied. The range
submitted to any processing as centrifugation, sifting or homogeniza- of temperature was chose to observe the gabiroba pulp behavior sub-
tion, in order to keep it as close as possible as it is found in the fresh mitted to cooking step followed by cooling, in order to simulate the
fruit. Generally in the literature, the studies related to shear thinning conditions used in jam manufacturing.
behavior in the steady-state shear properties of fruit pulps previously Fig. 4B shows G′ around 10,000 Pa higher than G″ around 3500 Pa,
submitted to processes to obtain a homogeneous pulp before per- with the moduli values stable throughout the heating-cooling cycle
forming the rheological measurements, as showed by açai (Euterpe (5 °C–95 °C). The data obtained for gabiroba pulp characterized the
oleraceae Mart.) (Tonon et al., 2009), siriguela (Spondias purpurea L.) predominance of elastic behavior, like a gel, and showed the thermal
(Augusto et al., 2012) and araçá (Psidium cattleianum sabine) (Haminiuk stability of the pulp at a wide range of temperatures, reflecting low
et al., 2006). The processing adopted by these authors (Haminiuk et al., internal structure changes in the temperature range analyzed.
2006; Tonon et al., 2009; Augusto et al., 2012) may promote changes in The thermal stability of gabiroba pulp indicates that the pulp can be
the rheological behavior. used for different applications involving heating, such as jam and fruit
filling in bakery products. In addition, it shows that the gabiroba pulp is
suitable for pasteurization, which is generally done from 60 °C to 100 °C
3.4. Dynamic rheology properties of gabiroba pulp
to reduce the growth of microorganisms, as well as extending shelf life
and delaying deterioration in industrialized fruit pulp (Saeeduddin
The dynamic viscoelastic properties of gabiroba pulp were eval-
et al., 2015).
uated by elastic (G′) and viscous (G″) moduli as a function of frequency
The stability of gabiroba pulp was also evaluated using a freezing
(Fig. 4A). Both moduli had a slight frequency dependence, with G′
test (Fig. 4C). The freezing test is a way to simulate the conditions used
exceeding G″ at all the frequencies analyzed (0.01–100 Hz). G′ in-
for pulp storage. In this test, G′ was determined throughout the heating-
creased from 3300 Pa to 13,500 Pa and for G″ from 900 Pa to 6000 Pa at
cooling cycle between −10 °C and 25 °C, at a constant cooling rate of
0.01 and 100 Hz, respectively. The values of G′ higher than G″ char-
0.5 °C min−1 and constant frequency of 1 Hz, using geometry with a
acterize the gabiroba pulp as a material with gel behavior. This beha-
grooved surface.
vior, obtained by a dynamic oscillatory system, can be attributed to the
Fig. 4C shows, upon cooling, a constant value of G′ around 7000 Pa
chemical structure of gabiroba pulp, more specifically the 6.5–8.5%
from 25 °C until −10 °C. Suddenly, a large increase of G′ (800,000 Pa)
pectin content (Santos et al., 2012; Barbieri et al., 2017) and other
was observed at −6 °C. The abrupt increase of G′ demonstrates the li-
polysaccharides present in the gabiroba pulp. The gel behavior has been
quid-solid phase transition of the water particles present in the pulp, by
reported for other pulp fruits, such as jabuticaba (Sato & Cunha, 2009),
which it was possible to determine the freezing point of gabiroba pulp.
siriguela (Augusto et al., 2012), and açai pulp (Tonon et al., 2009).
Upon heating, a large decrease of G′ (from 800,000 to 5000 Pa) was
In order to investigate the thermal stability of the gabiroba pulp,
observed on a smaller range of temperatures (from −2 °C until 0.3 °C),
temperature sweeps at a constant frequency of 1 Hz were performed. In

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compared to that of the cooling cycle. After that, G′ remained constant exhibited a yield stress minimum of approximately 108 Pa to initiate
(around 5000 Pa) until the end of the temperature sweep (0 °C–25 °C). the flow. The existence of yield stress in the flow of a material indicates
Meanwhile, the mechanical spectrum recorded after 0 °C at both cycles, that there is a cross-linked structure or other interactive structure that
heating/cooling, demonstrated the constant values of G′ throughout the must be broken down before flow can occur at an appropriate rate. In
temperature sweep (0 °C–25 °C). This behavior during the freezing test this type of material, the shear stress curve does not begin at the origin
demonstrates that the macromolecular characteristics of the gabiroba of the shear stress/shear rate plot and is concaved downwards (Canet,
pulp remain stable even after freezing and thawing, suggesting that the Alvarez, Fernández, & Luna, 2005; Sun & Gunasekaran, 2009).
freezing process can be used as a process of storage and preservation of The rheological behavior described by the flow curves was fitted to
gabiroba pulp without changes in the pulp’s rheological properties. the Herschel-Bulkley model with an obtained R2 value of 0.987, similar
In addition, the results obtained for gabiroba pulp by the tem- to mango jam (Basu & Shivhare, 2010), with R2 values ranging between
perature sweep during the freezing and thawing tests through rheolo- 0.818 and 0.996, and apple jam (Tan et al., 2014), with R2 values
gical analysis showed that the heating-cooling cycle can be used as a ranging from 0.891 to 0.998.
way to monitor the effects that the freezing process causes in the vis- By using the Herschel-Bulkley model, the parameters, such as τ0
coelastic behavior of the fruit pulp. (yield stress), K (consistency coefficient), and n (flow behavior index),
may be determined, indicating the extent of deviation from Newtonian
behavior (Steffe, 1996; Rao, 2007). The yield stress obtained for ga-
3.5. Steady-state shear properties of gabiroba jam
biroba jam was (τ0) 32.27 Pa. The K value of 39.40 Pa.sn and the n value
of 0.57 (n < 1) indicate that gabiroba has a shear thinning behavior.
The gabiroba pulp was characterized as having a gel behavior
In relation to K, the higher its value, the more consistent the jam is
(Fig. 4A) and thermal stability in a wide range of temperatures
(Steffe, 1996; Rao, 2007); the K value found for gabiroba jam
(Fig. 4B), demonstrating that this pulp has favorable rheological and
(39.40 Pa.sn) at 25 °C was greater than that described for rose hip
physico-chemical properties for its use as raw material in food products.
marmalade (17.6 Pa.sn) at 25 °C (Sagdic, Toker, Polat, Arici, & Yilmaz,
Therefore, a gabiroba jam formulation was developed using the ga-
2015) and within the range (21.0–73 Pa.sn) shown by Falguera et al.
biroba pulp and the rheological properties of the jam were investigated.
(2010) for peach jam at 20 °C, for which the K value varied according to
The steady-state shear properties of gabiroba jam were analyzed. As
the ingredients of their formulations.
have been already pointed out by other authors, this measurement in a
Fig. 5B shows the gabiroba jam viscosity as a function of shear rate.
structured product is important to establish a quality control method,
The shear thinning behavior was observed as the apparent viscosity
for processing calculations and product development (Basu et al., 2010;
decreased and the shear rate increased. The viscosity curve showed a
Falguera, Mengual, Vicente, & Ibarz, 2010; Gao, Yu, Zhang, Xu, & Fu,
Newtonian plateau at a low shear rate (0.01–0.02 s−1) with an apparent
2011; Tan, Cui, Lu, Zhao, & Wang, 2014).
viscosity of 2000 Pa. When analyzed at 50 s−1, the apparent viscosity
The flow behavior of gabiroba jam was evaluated at 25 °C (Fig. 5A).
was 8.3 Pa s, higher than the apparent viscosity of the peach jam
The shear stress rose with increases in the shear rate and the sample

Fig. 5. Influence of shear rate on the flow curve (A) and viscosity curve (B) of gabiroba jam (0.01–100 s−1) at 25 °C. (C) Frequency sweep (0.01–10 Hz) at 25 °C,
showing the effect of storage time on rheological behavior of gabiroba jam. Elastic modulus (G′, full symbols) and viscous modulus (G″, open symbols) (D) Elastic
moduli (G′, full symbols) and viscous moduli (G″, open symbols) as a function of temperature for heating and cooling cycles (5–95 °C) of gabiroba jam, with a
constant temperature rate of 1 °C min−1 at 1.0 Hz and 1.0 Pa.

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S.F. Barbieri et al. Food Chemistry 263 (2018) 292–299

(3.5 Pa s) (Falguera et al., 2010). The shear thinning behavior was also In addition, hydrophobic interactions are promoted by a high co-
observed in other fruits jams, such as mango (Basu & Shivhare, 2010) solute (sucrose) concentration that decreases the water activity re-
and apple jam (Tan et al., 2014), as determined by the flow curve. sulting in increased interactions between the pectin chains (Fu & Rao,
2001; Chan et al., 2017).
3.6. Dynamic rheology properties of gabiroba jam Furthermore, since gabiroba pulp exhibits elastic gel behavior and
thermal stability (Fig. 4B), the concentrations of gabiroba pulp particles
The determination of jams’ viscoelastic characteristics is important may also influence the rigidity of the three-dimensional network
for suitable design and handling processes; therefore the dynamic vis- formed by the HM pectin present in the jam. This effect may be due the
coelastic properties of gabiroba jam were evaluated by frequency sweep presence of fruit particles replace water in the final composition of the
(Fig. 5C). Elastic (G′) and viscous (G″) moduli increased with increasing composite gels (Genovese et al., 2010). The decrease of water activity
frequency and both demonstrated a dependency on frequency. For ga- favors the hydrophobic interactions between pectin chains, increasing
biroba jam, the G′ values were higher than the G″, which is the typical the strength of the gel network in gelation process jam.
behavior of gels.
The effect of storage time on the rheological properties of gabiroba
jam was also analyzed by frequency sweep at 25 °C. At the initial time, 4. Conclusions
just after formulation (time 0), G′ and G″ values were approximately
1300 and 600 Pa, respectively, at frequency of 1.0 Hz. The values of This study showed, through ultrastructure, sedimentation and
both moduli remained very similar to the jam at time 0, even after rheological analyses, the potential of gabiroba pulp for consumption in
storing the jam for 6 and 22 months (Fig. 5C), demonstrating the natura and for use as raw material in the development of food products.
maintenance of its rheological properties. The pomegranate jelly Gabiroba pulp analyzed by SEM presented a heterogeneous ultra-
showed stable rheological characteristics for 8 weeks in relation to the structure with a denser area formed by a compact mesh and a porous
effect of storage time (Ventura et al., 2013). These results obtained for interface containing fibers. The fibers’ presence promoted a slip effect
the gabiroba jam suggest that the gabiroba jam can be stored for a long when the gabiroba pulp was subjected to shear; however, when the
period while maintaining its rheological characteristics, which is im- pulp, both undiluted and diluted in water, was analyzed through the
portant for jam formulations that must maintain the gel behavior. sedimentation process, it was observed that the swelling capacity of
As a jam goes through temperature variations from its manufacture fibers increased water retention, preventing the sedimentation of the
to storage and commercialization, the rheological properties of ga- pulp.
biroba jam are evaluated as a function of temperature for heating and The dynamic viscoelastic properties of gabiroba pulp showed that
cooling cycles (5–95 °C) at a constant frequency of 1 Hz (Fig. 5D). the pulp presents a gel behavior and it is thermally stable in the tem-
During the heating cycle (from 5 °C to 95 °C), a decrease of G′ (from perature range of 5–95 °C. The mechanical spectrum recorded after
664 ± 72.4 Pa to 494 ± 65.5 Pa) and G″ (from 298 ± 122.3 Pa to heating/cooling cycles (−10 to 25 °C) showed that the macromolecular
155 ± 24.8 Pa) moduli was observed. characteristics of the gabiroba pulp remain stable even after the process
However, during the cooling cycle (from 95 °C to 5 °C), higher va- of freezing and thawing. Thus, it was demonstrated that the gabiroba
lues of G′ (1253 Pa) and G″ (610 Pa) moduli were observed, compared pulp can be preserved and stored by freezing and that, even after
to both moduli values at 5 °C during the heating cycle (G′ 664 Pa; G″ thawing, the viscoelastic properties of the pulp are maintained.
298 Pa), demonstrating a temperature dependence of G′ and G″ The flow behavior of a gabiroba jam, developed using pulp as raw
throughout the heating-cooling cycle. The same rheological behavior as material, was analyzed and the jam exhibited a yield stress minimum to
a function of temperature was also observed by Garrido, Lozano, and initiate the flow. The jam had a shear thinning behavior described by
Genovese (2015) in the cooling of apple jelly (90 °C–20 °C) and by the Herschel-Bulkley model. The mechanical spectrum and thermal
Genovese, Ye and Singh (2010) in a mixture of high methoxyl (HM) stability analysis showed that the gabiroba jam presented typical be-
pectin and apple particles. havior of gel, which was not modified after a storage period of
The decrease of both moduli during the heating cycle can be related 22 months. The obtained results indicate that gabiroba jam may be a
to behavior of the components present in the jam, such as the pectins, way to use and preserve gabiroba pulp. Also, the production of jam
which are the major polysaccharide in the gabiroba pulp (Barbieri could be an additional source of income for rural farmers in the regions
et al., 2017). In addition, commercial high methoxyl pectin (HM pectin) where gabiroba fruit is found, encouraging the preservation of this
was used to prepare the jam. HM pectins are widely used in jam for- native Brazilian species.
mulations in order to increase the firmness or strength of the gels, with
a reinforcing effect on the structure of the jam (Basu & Shivhare, 2010; Conflict of interest statement
Garrido et al., 2015). Depending on the temperature, the junction zones
of pectin network are stabilized by different interactions, which can The authors declare that they have no conflict of interest.
affect the network structure and the viscoelastic behavior (Lopes &
Gonçalves, 1994). The highest temperature increased the mobility of
the pectin chains and this behavior can be visualized by decreasing G′ Acknowledgements
and G″ moduli (Genovese et al., 2010; Kastner et al., 2014; Chan, Choo,
Young, & Loh, 2017). The authors gratefully acknowledge the following Brazilian agen-
The gelation process in jams occurs spontaneously during cooling cies for financial support: National Council for Scientific and
from the solution-state at high temperature (cooking process) and can Technological Development – CNPq, the Araucaria Foundation and the
be related to gelation process of HM pectin that occurs by formation of Ministry of Science and Technology. J.L.M.S. and C.L.O.P. are research
junction zones between juxtaposed pectin chains. The formation of members of the CNPq Foundation (No 476950/2013-9; 308296/2015-
junction zones is stabilized by hydrophobic interactions between the 0, 305051/2015-6). S.F.B. is the beneficiary of a PhD scholarship from
methoxyl groups and hydrogen bonds between protonated carboxyl and CNPq Foundation, Brazil (No 140774/2014-9). The authors would like
hydroxyl groups (Fu & Rao, 2001; Rao, 2007). Hydrogen bonds are to Federal University of Paraná – UFPR, Microscopy Center of UFPR,
favored at low pH, promoted by the addition of citric acid in the jam. Brazilian Agricultural Research Corporation/Embrapa Forestry,
The acidic medium result in protonation of the free carboxyl groups of Professors Rilton Alves de Freitas and Fernanda Fogagnoli Simas,
galacturonic acid units, minimising the electrostatic chain repulsion Pauline Laís Nasatto PhD and Alex Siqueira Santos for some experi-
(Kastner et al., 2014; Chan et al., 2017). mental contributions.

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