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Food Hydrocolloids 122 (2022) 107048

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Food Hydrocolloids
journal homepage: www.elsevier.com/locate/foodhyd

Physico-chemical properties and filmogenic aptitude for edible packaging


of Ecuadorian discard green banana flours (Musa acuminanta AAA)
Diego Salazar a, d, **, Mirari Arancibia a, Diana Lalaleo a, Roman Rodríguez-Maecker b, M.
Elvira López-Caballero c, *, M. Pilar Montero c
a
Facultad de Ciencia e Ingeniería en Alimentos, Universidad Técnica de Ambato, Av. Los Chasquis y Rio Payamino, Ambato, Ecuador
b
Departamento de Energía y Mecánica, Carrera de Petroquímica, Universidad de Las Fuerzas Armadas - ESPE, Latacunga, Ecuador
c
Instituto de Ciencia y Tecnología de Alimentos y Nutrición (ICTAN-CSIC), Calle José Antonio Novais 10, 28040 Madrid, Spain
d
Facultad de Veterinaria, Universidad Complutense de Madrid, 28040, Madrid, Spain

A R T I C L E I N F O A B S T R A C T

Keywords: Physico-chemical, functional properties, and filmogenic characteristics were determined in pulp (P) and whole
Green banana flour (W) banana flours (BF), pretreated or not (preT and unT, respectively) with sodium metabisulfite, obtained from
Rejected banana cultivars of Ecuadorian Musaceae: Musa acuminata AAA. The proximal composition revealed a high content of
Physico-chemical
fat, protein, ash, and fiber in whole banana flours, while the total starch and amylose content was greater in pulp
Functional properties
Filmogenic suspension
flours. The starch granules of both pulp and whole green banana flours presented an elongated and lenticular
Rheological properties sizes and shapes, which could be related to the amount and variations in amylose and amylopectin structure in
the raw materials. Pretreatment with metabilsulfite favors the increase in L* and b* parameters, while a* is
reduced; likewise, the presence of the peel tends to darken the untreated flours. Water absorption, solubility and
swelling capacity rose above 70 ◦ C, matching the gelatinization temperature observed by DSC (74–78 ◦ C). The
temperature of gelatinization was higher for the pretreated whole banana flour, noticeably, the highest enthalpy
ΔHgel (32.23 Jg-1) corresponded to the untreated whole banana flour. All banana flours had the ability to form
filmogenic suspensions that showed a similar pseudoplastic behavior regardless of the flour composition, except
for the pretreated pulp flour, which showed less shear thinning. The viscosity recovery capacity with the decrease
in temperature was almost total in the untreated samples, while in the treated samples was lower (~20%). The
higher amount of amylopectin favored the viscoelastic properties in the filmogenic suspension, while the lower
content of this compound diminished these properties. For the aforementioned, green banana flours are an
ingredient of interest and their ability to form filmogenic solutions can be a good alternative for its subsequent
industrial application.

1. Introduction management and distribution, around 25% of the total output is rejec­
ted for exportation. The main reason is that bananas do not comply with
Banana crops have become the base of the economy of some coun­ the class “A" premium quality requirements: variety, number and size of
tries such as India, Brazil, Costa Rica, Colombia, Ecuador, Philippines, fingers per hand, color, appearance, caliber, packaging, and phytosa­
China (Scott, 2020), and is one of the most consumed fruit in the world; nitary conditions (Sartori & Menegalli, 2016; Stanley, 2017).
in fact, it is the fourth most important food crop after rice, wheat and In general, rejected bananas are destined for local human con­
maize (Bruinsma, 2017). In 2018, the gross volume of world banana sumption, animal feed, raw material for industry, or waste used as fer­
exports reached a record of 19.2 million tons; in this year, Ecuador, the tilizer. Ripe bananas are used to produce, among others, syrup,
leading exporter of the Cavendish crop, supplied 6.7 million tons, rep­ dehydrated sliced, frozen flakes, beverages (both fermented alcoholic
resenting 32% of the world trade (FAO, 2019). However, despite the and non-alcoholic), juices, nectars, vinegar, banana powder, jellies, jam,
investment to improve/optimize banana production, post-harvest compotes, snacks (Girotto et al., 2015; Yusuf et al., 2016), while the use

* Corresponding author.
** Corresponding author. Facultad de Ciencia e Ingeniería en Alimentos, Universidad Técnica de Ambato, Av. Los Chasquis y Rio Payamino, Ambato, Ecuador.
E-mail addresses: dm.salazar@uta.edu.ec (D. Salazar), elvira.lopez@ictan.csic.es (M.E. López-Caballero).

https://doi.org/10.1016/j.foodhyd.2021.107048
Received 30 April 2021; Received in revised form 13 July 2021; Accepted 16 July 2021
Available online 19 July 2021
0268-005X/© 2021 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
D. Salazar et al. Food Hydrocolloids 122 (2022) 107048

of unripe bananas has mainly been focused on the production of flour by power and amylose-amylopectin entanglement (Hernandez-Perez et al.,
drying, however, this use is not widespread, at least by now. 2021) and thus the physico-chemical modification could be affected by
Banana flour is constituted by starch, protein, lipids, minerals and the functionally of the molecules.
vitamins (Chávez-Salazar et al., 2017). Likewise, most of the flours are This study aimed to evaluate the physico-chemical and functional
usually made from pulp, but the peel represents 40% of the total fresh properties of flours from rejected unripe green bananas from Ecuador as
weight of the product, and it is mainly constituted by dietary fiber, well as their filmogenic aptitude in order to provide knowledge for
protein, and lipids (Oliveira et al., 2018). Browning phenomena are potential applications.
usually observed in bananas during drying to obtain flours. In some
cases and in order to avoid it, a pretreatment with diluted acids (Anyasi 2. Material and methods
et al., 2017; Bakare et al., 2017) and other compounds such as sodium
metabisulfite (Bakare et al., 2017; Haslinda et al., 2009) is performed. 2.1. Banana flours
However, there are hardly any studies evaluating the effect of different
treatments that may avoid browning. Green bananas (Musa acuminata AAA), which did not satisfy the
Nutritionally, unripe whole banana flour is beneficial for health due minimum requirements for export, were purchased from crops in
to its high content of resistant starch, which generates a low blood Valencia, Los Rios (Ecuador). Bananas were cleaned and washed with
glucose response since it is not digested, but fermented in the colon by water. Two types of slices of ~3 mm were produced: the first one con­
the bacterial microflora (Falcomer et al., 2019; Wang et al., 2015). sisted of peeled slices (pulp banana) that were either immersed into
Moreover, the consumption of immature bananas enhances the feeling sodium metabisulfite solution (0.5% w/v) for 10 min (PF-preT) or did
of satiety since unripe bananas act as dietary fiber during intake not receive any treatment (PF-unT). Similarly, the second type were
(Demitri et al., 2017; Monteiro et al., 2016), so their consumption and whole banana slices (pulp and peel) with metabisulfite (WF-preT) or
use as a food ingredient could be of great interest. The banana flour without metabisulfite (WF-unT). After drained, slices were dried at
composition will determine the functional properties (from a techno­ 60 ◦ C for 6 h in a convection oven dryer (Gander MTN, USA) until
logical and nutraceutical point of view), and therefore, the most suitable moisture values were constant. Finally, the dried product was milled to
applications of the flour. The composition varies remarkably, not only produce a fine powder. All samples were hermetically packed and stored
by the state of maturity, but also by the different cultivars, geographical at room temperature until further analysis.
locations, and regional climatic factors. Moreover, harvesting seasons
affect the physico-chemical composition -especially regarding starch 2.2. Proximate composition of flours
content- and the properties of bananas from different origins, for
example, South Africa (Anyasi et al., 2017), China (Pereira et al., 2020), Moisture, fat content, crude protein, ash and crude fiber, were
Thailand (Orsuwan & Sothornvit, 2017), Vietnam (Hung et al., 2013), determined according to AOAC methods (AOAC, 2000). Carbohydrate
Indonesia (Marta et al., 2019), Mexico (Juarez-Garcia et al., 2006), content was determined by difference. The analyses were performed in
Brazil (Martins et al., 2019), where some compounds may even be ab­ triplicate.
sent, depending on the banana variety (Marta et al., 2019). In this re­
gard, there are no studies on the immature Musa acuminata variety from
2.3. Total starch content
Ecuador, neither for whole bananas, nor for pulp or peel independently.
Therefore, because of the variations of flour quality, which depend on
The total starch content was carried out according AOAC
the geographical location, it is important to study banana cultivars from
945.37–1945 method (AOAC, 2005). Approximately 2.5 g of each flour
Ecuador to evaluate their characteristics and hence, their functional
were weighed and transferred to a centrifuge tube with 25 mL 0.3 M
properties, with a view to future applications.
HCl. The samples were taken to a boiling water bath for 15 min with
Unripe banana flour has an unexplored potential due to its functional
agitation. After cooling at room temperature, 1 mL of Carrez-1 solution
properties. Moreover, most studies on unripe banana flours deal with
and 1 mL of Carrez-2 solution were added. The mixture was centrifuged
starch from pulp and peel flours separately. Nevertheless, it would be
(Rotina 380, Germany) at 606 g for 5 min, and the supernatant was
very interesting to evaluate the behavior of whole fruit (pulp-peel) flours
transferred to a polarization tube. The starch content was measured
as reported by Bi et al. (2017) to study the potential of flour/starch from
using a polarimeter (Polax-2L, ATAGO, USA). The amount of starch was
different varieties of banana from China (Musa Dwarf Red babana Var.
calculated by using equation (1).
Guihongjiao N◦ 1, Musa ABB Pisang Awak. Jinfen N◦ 1 and Musa AAA
Cavendish Var. Williams B6) as a substitute for isolated starch in food A = (a − b)*F Eq. (1)
preparations. The use of whole banana flours has been evaluated, for
example, in different properties of fat-reduced frankfurters (Musa acu­ where A is the percentage of starch content; a is the optical activity
minata Colla cv. Cavendish, China) (Pereira et al., 2020); for the pro­ (specific rotation); b is the optical activity of the blank, and F is the
duction of powder blends rich in antioxidant properties from Musa potato starch factor (5.501). The tests were carried out in triplicate.
acuminate Colla x Musa balbisiana Colla (Brazil) (Martins et al., 2019);
the elaboration of candy from Musa paradisíaca (Brazil) (Oliveira et al., 2.4. Amylose content
2018) or its filmogenic properties to develop films of green banana flour
(Musa sapientum Linn, from Thailand) (Orsuwan & Sothornvit, 2017). In The amylose content was determined using the iodine colorimetric
this connection, the rheological behavior of filmogenic suspensions and method (Ortega & Echeverria, 2016). One hundred milligrams of the
the interactions between the components offers information on funda­ sample were transferred to a 100 mL volumetric flask followed by the
mental aspects of the materials, compatibility and limitations, and the addition of 1 mL of ethanol (95%) (Merck, Germany) and 10 mL 1.0 M
different technologies for future applications (Hernandez-Perez et al., NaOH (Merck, Germany); distilled water was added to fill up the volume
2021; López et al., 2015), mainly as coatings or films. In addition to the to 100 mL and then mixed. The solution was maintained at room tem­
applications, viscosity properties through rotational tests, or gelling perature (18–20 ◦ C) for 24 h. An aliquot of 2.5 mL of the prepared so­
properties through viscoelastic tests, can be also evaluated. Rotational lutions was mixed with 1.0 mL of 1.0 M HCl (Merck, Germany) and 1 mL
tests evaluate the rheological behavior of starch pastes, being able to of iodine solution (2%) and left to stand in total darkness for 20 min to
simulate conditions close to industrial processing, when for example, a subsequently quantify the amylose content using a spectrophotometer
high shear stress is applied (López et al., 2015). The rheological (Shimadzu UV-2600, Japan) at 620 nm, based on a standard calibration
behavior of gelatinized starch is influenced by granular size, swelling curve of amylose (Sigma-Aldrich Chemical Co. St. Louis, USA). The tests

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D. Salazar et al. Food Hydrocolloids 122 (2022) 107048

were carried out in triplicate. determine the amount of water necessary to perform the experiment due
to the nature of the material and the rate of water absorption. Then,
approximately 10 mg of banana flour (dry weight basis), was weighed
2.5. Physico-chemical properties of flours into aluminum pan and 55 μL of distilled water was added. An empty
pan was used for control purposes. The cups were hermetically sealed
2.5.1. Color and held for 24 h at room temperature (~20 ◦ C). Finally, the sample was
Color on flours was measured by a colorimeter (ColorFlex EZ, placed inside the DSC equipment and heated from 25 to 90 ◦ C at a
HunterLab, USA) using CIELAB® color scale with the parameters L * heating rate of 10 K min− 1, as previously described for green banana
(lightness), a* (red/green), b* (yellow/blue). The polar coordinate or flour (Pacheco et al., 2019; Prachayawarakorn et al., 2015). Nitrogen
saturation Chroma C* was calculated using the expression C* = √ (a2 + was used as a purge gas at a rate of 50 mL min− 1. The tests were carried
b2), Hue angle (◦ H) with the equation (◦ H) = arctg (b*/a*), and out in triplicate.
whiteness index (WI) with the equation WI = L- 3b + 3a. The flour
samples were placed in small petri dishes at a depth of 0.5 cm to obtain a 2.5.6. Swelling and solubility power
uniform distribution. Measurements were made in 5 sections of the box. Solubility and Swelling measurements were performed according to
At least 25 measurements were made in different parts of the sample in the methodology described by Kusumayanti et al. (2015). A suspension
triplicate. of flour in water (~1% w/v) was prepared and conditioned in a thermal
bath at different temperatures: 50, 60, 70, and 80 ◦ C for 30 min with
2.5.2. Granulometry constant agitation and finally, cooled at room temperature and centri­
The particle size was determined according to the Standard INEN fuged (Rotina 380, Germany) at 4865 g for 15 min. The supernatant was
NTE 0517 (2013) (INEN, 2013). One hundred grams of flour were placed separated, dried at 100 ◦ C for 24 h and weighed, as well as the precip­
in a set of 5 sieves (Tyler series, USA); the diameter consecutively itate (gel). Equations (2) and (3) were used for determination. The an­
decreased downward and the sieves were labeled from top to bottom: 40 alyses were performed in triplicate.
(420 μm), 60 (250 μm), 100 (149 μm), 140 (106 μm), 200 (75 μm) and
soluble ​ solids ​ weight ​ (g)
the pan collector. The sieves were mechanically vibrated in a sieve Solubility = Eq. (2)
sample ​ weight ​ (g)
shaker equipment (Porter Sand, USA) for 5 min and the flour retained on
each sieve, was carefully collected and weighed. The two parameters
​ gel ​ weight ​ (g)
used to measure size were uniformity index (UI) and fineness modulus Swelling ​ power =
sample ​ weight ​ (g) − soluble ​ solids ​ weight ​ (g)
(FM). The fineness modulus is defined as the sum of the fractions of the
weight retained on each sieve divided by 100; each fraction of retained Eq. (3)
weight was multiplied by a modular number in accordance with the size
of the sieve (sieve 40: factor 5, sieve 60: factor 4, sieve 100: factor 3, 2.5.7. Water absorption capacity (WAC)
sieve 140: factor 2, sieve 200: factor 1, pan collector: factor 0). Fineness The water absorption capacity (WAC) of the samples was determined
modulus of flours is classified as follows: 0–2 Fine, 2–4 Medium, and according to the Bryant and Hamaker (1997) method. A dispersion of
above 4 Coarse. Uniformity index determines the size of the fine, me­ flour (1% w/v) in water was prepared in a 500 mL centrifuge bottle,
dium, and coarse particles in the flours; this index is reported as g/10 g heated in a thermal bath at different temperatures: 50, 60, 70, and 80 ◦ C
of the sample for each of the different particle sizes, calculated by the for 15 min with constant stirring, and then centrifuged (D-78532, Het­
average of retention on different sieves (sieve 40–60 are coarse, sieve tich®, Germany) at 1000 rpm for 10 min. WAC was expressed using
100–140 are medium, and sieve 200- pan collector are fine particles). equation (5), and the results were made in triplicate.
The measurement was made in triplicate. (
g ​ of ​ water ​ adsorbed
)
WAC (%) = *100 Eq. (4)
​ g ​ sample
2.5.3. Bulk density
The bulk density (BD) of flours was determined as described by
Gujska and Khan (1990). Inside a graduate cylinder, flour was added up 2.6. Filmogenic suspensions
to the 100 mL line, the bottom of the cylinder gently tapped 3 times until
there was no further diminution and weighed. The bulk density was 2.6.1. Preparation of filmogenic suspensions
calculated by dividing the flour mass (weight) by the flour volume in the Filmogenic suspensions were prepared with 5 g (of each flour) in
cylinder (Jinapong et al., 2008). The assays were made in triplicate. 100 mL of distilled water and heated to 80–90 ◦ C, with constant stirring
for 5 min. Subsequently, the temperature was reduced to 70 ◦ C, and
2.5.4. Scanning electron microscope (SEM) glycerol was added at 50% (w/w). Then the mixture was filtered and
The morphological analysis of flours was performed in a scanning immersed in an ultrasonic bath (Sonopuls HD 2070; DICSA, Germany)
electron microscope (SEM) (Vega 3, Tescan, USA). The organic samples for 15 min to eliminate bubbles.
were placed on the SEM stub provided with double-sided conductive
carbon tape. The samples were then sputter-coated with gold. Finally, 2.6.2. Density and pH of fimogenic suspensions
each sample was observed at 3Kv in the microscope, with a field of view The density of the suspensions was determined using a pycnometer,
of 253 μm and a magnification of 546x (as maximum diameter of the according to Lau et al. (1997). The tared pycnometer was filled with
image displayed). distilled water, avoiding the formation of bubbles, and weighed. Then,
the pycnometer was weighed with the filmogenic suspension of banana
2.5.5. Differential scanning calorimetry flours. All determinations were made at 25 ◦ C. The determinations were
Differential scanning calorimetry (DSC) was made in DSC 3 equip­ made in triplicate and the density was calculated based on equation (5).
ment (Mettler Toledo, USA). Previously, several tests were carried out to

sample ​ weight ​ (g) ​ H2 O(25◦ C) 0, 0012∗[sample ​ weight ​ (g) − water ​ weight(g)]


ρ= ∗ ∗ Eq. (5)
water ​ weight ​ (g) ​ H2 O(4◦ C) water ​ weight ​ (g)

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2.7. Experimental design

The pH of the suspensions was determined following the methodol­ Results were analyzed by one-way ANOVA. Means were tested with
ogy described by Orsuwan and Sothornvit (2017). The tests were carried Tukey’s Multiple Comparison Test, with a significance level α = 0.05
out in triplicate. using GraphPad Prism v5.03 (GraphPad Software, San Diego, California,
USA).
2.6.3. Rotational and oscillatory rheological tests of filmogenic suspensions
The rheological tests were performed in a Compact Modular 3. Results and discussion
Rheometer (Anton Paar MCR302, Austria) using a concentric cylinder
system (CC27) for rotational tests and cone-plate PP25 (gap = 1 mm) for 3.1. Composition of flours
oscillatory tests. The data obtained were analyzed with the team’s Rheo
Compass software. The results of the proximal composition are shown in Table 1. The
pretreated pulp flour showed lower moisture than the other samples (P
2.6.3.1. Rotational test. The flow behavior and the apparent viscosity < 0.05), which could be attributed to the fact that the salt captures water
were evaluated in a gradient of cutting speed from 0 to 1000 s− 1 and thus, desiccation is easier. Moisture content can vary with the
following the methodology proposed by Glorio Paulet et al. (2009) at a drying process and storage conditions (Bakare et al., 2017; Santos et al.,
controlled temperature of 25 ◦ C. Gelation kinetics were analyzed in a 2010). Moisture values in the present work were in accordance with the
temperature sweep; the measurements were made in the heating ramp of quality limits for flours (% H < 14%) (CODEX STAN 152–1985)
25–90 ◦ C and cooling ramp of 90 to 25 ◦ C, with a constant heating rate (CODEX, 1985). Similar results were obtained by Espitia-Pérez et al.
and oscillation frequency of 1 Hz. (2013), who found 11.6% moisture in reconstituted composite (pulp and
The flow curves were fitted to rheological models (Ostwald de Waele, peel) banana flours of Musa ABB Simmonds variety from Colombia.
Herchey-Bucley, Newtonian and Casson) by calculating linear re­ However, Marta et al. (2019), found differences in pulp flour moisture
gressions to obtain the coefficients and exponents of the equations from (8–6.92%) in four cultivars from Kapas, Nangka, Ambon and Kepok
empirical models. The criterion for selecting the model that best (Indonesia).
described the rheological behavior of the suspensions was based on their Fat content was low (<1%) in all samples (Table 1). Whole banana
highest correlation. flours showed a significantly higher lipid content than pulp flours (P <
0.05) due to a greater amount of lipids as well as liposoluble substances,
2.6.3.2. Oscillatory test. The viscoelastic behavior analysis of the sus­ mainly carotenoids, present in the peel (Emaga et al., 2007; Juar­
pensions was carried out using dynamic mode tests, by deformation ez-Garcia et al., 2006). In this connection, pulp flours contained around
sweeps at a frequency of 1 Hz and frequency scans in a range of 1–10 Hz, 0.53% fat in green banana (Musa acuminata, group AAA) (Torres et al.,
at controlled temperature (25 ◦ C). The registered dynamic rheological 2005). Likewise, Haslinda et al. (2009) found higher values than those
parameters were: linear viscoelasticity range (RVL), complex modulus of obtained in the present work, in pulp and peel flour (1,94%) in green
shear stress (G*), storage modulus (G′ ), and the loss modulus (G′′ ). The banana (Musa acuminata x balbisiana Colla cv. Awak) from Malaysia. It
methodology used was based on the method proposed by Guerra-­ seems the results may vary depending on the variety, geographical area
DellaValle et al. (2009). The tests were carried out at least in triplicate. and maturity state.
The protein content was in a narrow range for all samples (P < 0.05).
Juarez-Garcia et al. (2006) obtained similar values (3.3%) in unripe
banana pulp flour (Musa paradisiaca L.) from Mexico and established
that the banana variety influences the protein content, while the lower
Table 1 protein yield of the pulp might be related to the effect of salt stress. The
Composition and color characteristics of pulp and whole banana flours. slightly high protein content (P < 0.05) in the whole banana samples can
Component (%) Samples be related to the abundance in amino acids such as leucine, valine,
phenylalanine, and threonine in the peel (Blasco López & Montaño,
PF-preT PF-unT WF-preT WF-unT
2015; Espitia-Pérez et al., 2013). The varieties of Musa AAA in Indonesia
Moisture 9.96 ± 0.50a 11.73 ± 0.20b 11.13 ± 11.32 ± were different, having a lower protein content (2.0–2.9) (Marta et al.,
0.12b 0.17b
Fat 0.15 ± 0.02a 0.30 ± 0.03ab 0.96 ± 0.32b 0.87 ± 0.07b
2019), as the Musa varieties Ouro colatina (AAA), Nanica (AAA), Nanicão
Protein 3.41 ± 0.03a 3.43 ± 0.06a 3.73 ± 0.04b 3.53 ± (AAA), Prata Ana (AAB), Prata comun (AAB), Mysore (AAB), Maca (AAB)
0.14ab and Ouro da Mata (AAB), from Brazil (2.5–3.3%) used by da Mota et al.
Ash 2.64 ± 0.09a 2.42 ± 0.03b 3.96 ± 0.12c 3.76 ± 0.02d (2000). Higher amounts of protein were found in both pulp and whole
Fiber 1.28 ± 0.04a 3.11 ± 0.02b 3.19 ± 0.07b 3.51 ± 0.08b
banana flours (~6%) by Haslinda et al. (2009) in the banana variety
Carbohydrates 82.56 ± 79.01 ± 0.07b 77.03 ± 77.01 ±
0.05a 0.03c 0.06c Musa acuminata Colla Awak ABB from Malaysia, pretreated with 0.1%
Starch 78.21 ± 68.76 ± 0.01c 76.21 ± 72.48 ± (w/V) sodium metabisulfite. The ash content in pulp flours was lower
0,19a 0.03a 0.11b than in whole banana flours (P < 0.05). Moreover, pulp or whole banana
Amylose 17.98 ± 14.51 ± 15.22 ± 13.29 ± flours treated with metabisulphite showed slightly higher values (P <
0,14a 0,47bc 0,52b 0,26c
Amylopectin 60.23 ± 54.26 ± 0.47b 61.00 ± 59.19 ±
0.05) than their corresponding untreated counterparts (~8 and 5%,
0.90a 0.36a 0.33a respectively) (Table 1). Haslinda et al. (2009) found similar ash contents
L* 79.7 ± 0.60a 73.8 ± 0.36c 78.1 ± 0.45b 59.3 ± 0.6d in banana flours with and without peel, around 3.58%, and 2.46%,
a* 0.2 ± 0.13c 2.0 ± 0.06b 0.1 ± 0.01d 3.1 ± 0.14a respectively. These authors mentioned that the higher proportion of
b* 14.0 ± 0.41a 12.9 ± 0.45c 14.0 ± 0.56a 13.7 ± 0.30b
minerals could be attributed to sodium and calcium concentrations in

H 89.1 ± 0.22a 81.1 ± 0.35b 89.59 ± 77.3 ± 0.34c
0.70a the peel, which resulted in an almost four-fold increase in ash content
C* 14.0 ± 0.41a 13.0 ± 0.45a 14.0 ± 0.55a 14.1 ± 0.32a compared with the pulp alone.
WI 75.3 ± 0.47a 70.7 ± 0.57c 74.0 ± 0.63b 56.9 ± 0.61d Regarding fiber content, the values ranged from 1.28% to 3.51%
PF-preT: Banana pulp flour with sodium metabisulfite; PF-unT: Banana pulp (Table 1). In commercial Brazilian green banana flours, Vernaza et al.
flour without sodium metabisulfite; WF-preT: Whole Banana flour, with sodium (2011) reported values of fiber of 8.88%, and Juarez-Garcia et al. (2006)
metabisulfite; WF-unT: Whole Banana flour, without sodium metabisulfite. of 6.8%, in pulp banana flour (BF) obtained from unripe bananas (Musa
Different letters (a, b, c, d) indicate significant differences between samples. paradisiacal L.) from Mexico. Higher values than the abovementioned

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were found in the Awak variety (Brazil), where the fiber contents of the properties and rheological behavior of the flours, the amylopectin con­
flour were 7.53% and 11.27% for pulp and whole banana flours, tent of the samples was calculated, presenting lower values in the un­
respectively (Haslinda et al., 2009), and in some occasions up to 30% treated pulp flour (Table 1).
fiber has been found in banana (Musa paradisiaca L.) peel from Mexico
(Agama-Acevedo et al., 2016). The reported values were noticeably 3.2. Physico-chemical properties of flours
higher than those obtained in the present work, differences that might
be related to the variety of bananas used and the geographical area of According to Marta et al. (2019), to understand the different prop­
the crops. erties of the flours regarding the varieties of origin, it is necessary to
The non-fiber carbohydrate content is markedly higher in pulp flours focus on the properties of the starch and not of the flour, thus elimi­
(P < 0.05), corresponding to the lower content of fiber and ash of this nating the influences attributable to components that do not correspond
type of flour. The starch content in pulp and whole banana flours varied to starch. They also suggest that the differences could be mainly due to
from 68.76% to 78.21% (Table 1). These values were clearly lower than the different structures and morphologies that starch may present, and
those obtained by Haslinda et al. (2009) in banana (Awak ABB) pulp the lesser or greater presence of fiber. The composition and behavior of
flours (81.83%) and with the peel (81.55%). Also, Zhang et al. (2005) the flour will then be related to their technological aptitude. In Fig. 1,
reported that the average starch content in pulp and whole green banana the visual aspect of the 4 flours under study can be observed. Regarding
flours (Musa sapientum from Bangladesh) is 70%–80%, respectively. This the thickness of the granules, there are no differences to the naked eye;
same range was obtained in pulp flour of various varieties of Musa spp. however, there are differences in color. Flours from the pulp are lighter
from Indonesia (Marta et al., 2019). In the present work, in both types of than whole banana flours, so the addition of the peel makes the flour
flour (pulp or whole banana), washing with metabisulphite influences noticeably darker. Pretreatment with metabisulfite prevented browning
positively and significantly the starch content, because the inhibiting in both types of flour.
capacity that this compound has on the enzymatic activity could prevent
the splitting of the starch molecule in its fractions. The content of 3.2.1. Color characteristics
amylose in all samples ranged between 13.29% and 17.98%, being CIELab coordinates (L*, a*, and b*) are shown in Table 1. Values of
higher in the samples that only contained pulp flour. These results are luminosity (L*) are above 59. During the production of banana flours,
comparable with the 13.3% amylose content found by da Mota et al. color tends to darken because during drying, the Maillard reaction is
(2000) in pulp banana flour from different varieties of Musa genus in favored by glucose, fructose, and proteins in the banana peel (Alkarkhi
Brazil; however, the four varieties selected by Marta et al. (2019) from et al., 2011). The flours treated with sodium metabisulfite, regardless of
Indonesia, yielded around twice the values of amylose content the presence of the peel, showed the highest L* values (P < 0.05), not
(32.5-40-9). The lower content of amylose could be related to the high differing PF-preT and WF-preT by more than 1.6 units. However, the
fiber content of the peel. Since amylopectin content and the amylose: untreated flours showed lower lightness, and this fact was more pro­
amylopectin ratio are important to understand the physico-chemical nounced in whole banana flours, showing that the banana peel is darker

Fig. 1. Visual appearance of flours: A: Banana pulp with sodium metabisulfite (PF-preT); B: Banana pulp, without sodium metabisulfite (PF-unT); C: Whole Banana,
with sodium metabisulfite (WF-preT); D: Whole Banana, without sodium metabisulfite (WF-unT).

5
D. Salazar et al. Food Hydrocolloids 122 (2022) 107048

than the pulp and contributes to a certain darkening of the flours. (Anyasi et al., 2017). The metabisulfite pretreated flours had a
Similar L* values were obtained in banana pulp flour from Musa yellowish-white color (cream), while the lowest values were found in
acuminate pretreated with ascorbic, citric or lactic acid at different the untreated flours, especially in those that contained the peel (P <
concentrations (10–20 g/L); however, in pulp flour obtained from 0.05) (Table 1). Anyasi et al. (2017) also observed that a pretreatment
un-commercial varieties and pretreated in a similar manner, the L* was with organic acid solutions reduces discoloration. These results confirm
higher (79,3–84.7) (Anasi et 2017). L* values in pulp flour of plantains that the use of metabisulfite prevents color changes due to chemical and
from the Agbagba (81.30) and Obino L’ewai (82.03) varieties from enzymatic effects on the fruit during drying, even when the peel is
Nigeria, were found to be related with the degree of maturation (degree present.
1 in this case) (Falade & Oyeyinka, 2015). Ahmed (2020) obtained
slightly higher values (88.62) in the variety of Musa spp. AAA from a 3.2.2. Granulometry
commercial cultivar ‘Mountain’ in India, from green bananas pretreated The granulometric profile, determined by the fineness and unifor­
with citric acid (1%, 10 min) and dried at 55 ◦ C. mity indexes, is mainly related to grinding; this process influences the
Regarding a* the pretreated batches showed lower values than the intrinsic characteristics of the flour and therefore, the quality of the final
untreated ones (p < 0.05), exhibiting a clear effect against browning, product. The fineness index values were from 1.28 to 1.41, which
while for parameter b*, the yellowest values corresponded to pretreated determine that particle size and size distribution correspond to flours
samples (p < 0.05), due to the sodium sulfite pretreatment, which pre­ with fine particles (Table 2). The fineness index has a significant effect
vented color changes attributable to chemical and enzymatic effects on water absorption, considering that finer particles absorb more water
during the cutting and drying of the fruit (Jyothi et al., 2007). Due to its than thicker ones because there is more surface area to interact with
bleaching properties, sulfur dioxide allows obtaining flours with greater water molecules (Hoyos Sánchez et al., 2015). Kramadibrata et al.
luminosity, closer to white (100) (Br Sembiring et al., 2020). García-­ (2013) from Indonesia also reported a fineness modulus of 0.5 in the
Tejeda et al. (2011) observed b* values around 10 in unripe banana flour of unripe bananas, which corresponds to flour with fine particles
(Musa paradisiaca L from Mexico) starch treated with (NaOCl, 3%), similar to those of this work. The results do not show differences in the
similar to those obtained in this work. Higher values for a* were ob­ fineness index depending on whether the flour is from the whole banana
tained in pretreated banana pulp flour with different organic acids, or the pulp. The uniformity index shows that flours have a noticeably
being the most effective lactic and citric acids and the least ascorbic acid greater quantity of fine particles (P < 0.05) (Table 2), while there are no
(Anyasi et al., 2017). C* values showed low saturation (p < 0.05) in all significant differences between medium and thick particles. However, it
samples, while ◦ H values were higher in pretreated batches. Untreated is worth noting that the grinding process was similar for all samples, and
samples were located in the yellow-red quadrant, with a tendency to­ even though there are fractions of different sizes in the flours, no dif­
wards brown colors, attributable to the enzymatic browning of the fruit. ferences were found in the fineness index, except for WF-preT (P <
Alves et al. (2007) using unripe mixtures of Musa acuminata Colla and 0.05). The results of the present study show that flours are fine, in
Musa balbisiana Colla from Brazil, observed notably higher values of C* contrast with the findings of Bezerra et al. (2013) in green banana (Musa
(25.39–25.94) and H◦ (1.12–1.13) for pulp flour and whole banana cavendishii) flour from Brazil with and without the peel. These authors
flour, respectively (flours were obtained by freezing slices of the raw reported that the particle size was not uniform; the largest particles
material that were lyophilized later). Pretreated whole banana flour was obtained were in the range of 500 and 177 μm, which correspond to
settled in the yellow-green quadrant due to the banana peel pigments, medium and thick granule flours.
while pretreated pulp flour tended towards the yellow color (Table 1).
The white index measured the degree of deviation of the flours with 3.2.3. Bulk density
respect to a clean white, and it is used to determine consumer preference Bulk density is essential when flours need to be packed since volume
impacts handling, storage, transportation, and processing costs (Gupta
et al., 2018). In the current study, values ranged from 0.63 to 0.72 (P <
Table 2 0.05) (Table 2). Anyasi et al. (2017) in unripe Musa species (Williams,
Granulometry properties, bulk density and particle size distribution of pulp and Luvhele, Mabonde and Muomva-red) pretreated with ascorbic, citric, and
whole banana flours. lactic acids reported values of 0.66–0.84 g/cm3. However, Falade and
Properties PF-preT PF-unT WF-preT WF-unT Oyeyinka (2015) in banana flour varieties Agbagba and Obino L’ewai
obtained lower values (0.48–0.54 g/cm3). The bulk density may be
Fineness index 1.37 ± 1.40 ± 1.28 ± 1.41 ±
0,01a 0,01a 0,01b 0,01a
related to the amount of amylose and the amylose: amylopectin ratio,
Uniformity index Thick 2.16 ± 2.26 ± 2.01 ± 2.25 ± which favors compaction, and coincides with denser flour. On the other
(g/10 g sample) 0.07a 0.06a 0.01a 0.01a hand, density is higher when particles are not agglomerated and occupy
Medium 1.19 ± 1.10 ± 1.07 ± 0.98 ± a greater volume due to a low resistance to compaction; by contrast,
0.02a 0.06ab 0.01ab 0.01b
when the particles are agglomerated, they show a lower value of
Fine 6.66 ± 6.63 ± 6.92 ± 6.77 ±
0.05c 0.01c 0.01a 0.01b apparent density (Rayo Mendez, 2013). The particles that offer resis­
Bulk density (g/ 0.72 ± 0.68 ± 0.69 ± 0.63 ± tance to compaction and that present high friction, result in minimum
cm3) 0.04a 0.02ab 0.01ab 0.01b bulk densities considering the fact that when a group of solids is placed
Particle Sizea (%) 10–20 μm 6.1 ± 3.0 ± 5.5 ± 11.2 ±
in a specific volume (container, cylinder), they tend to organize them­
0.04b 0.04d 0.03c 0.06a
20–30 μm 9.1 ± 8.9 ± 11.1 ± 38.8 ±
selves randomly, maintaining empty spaces between them (Abdullah &
0.06c 0.05c 0.07b 0.06a Geldart, 1999).
30–40 μm 30.3 ± 26.4 ± 16.6 ± 19.4 ±
0.07a 0.05b 0.04d 0.10c 3.2.4. Scanning electron microscope (SEM)
40–50 μm 36.3 ± 38.2 ± 50.1 ± 30.5 ±
In the electron micrographs, the most abundant particles corre­
0.04c 0.09b 0.07a 0.03d
>50 μm 18.1 ± 23.5 ± 16.7 ± – sponded to the starch granules, which presented different morphology,
0.05b 0.09a 0.09c as observed using the SEM (Fig. 2). In whole banana flours, the starch
granules were bound together, close to other structures such as fiber and
PF-preT: Banana pulp flour with sodium metabisulfite; PF-unT: Banana pulp
flour without sodium metabisulfite; WF-preT: Whole Banana flour, with sodium protein that are part of the flours that contain banana peel (Alba et al.,
metabisulfite; WF-unT: Whole Banana flour, without sodium metabisulfite. 2018; Martins et al., 2019; Savlak et al., 2016). The starch granules
Different letters (a, b, c, d) indicate significant differences between samples. tended to differ morphologically, showing predominantly an ellipsoidal
a
Particle size is grouped in intervals of sizes of long diameter measured in μm. flattened shape, showing granules in the range of 9–53 μm (long

6
D. Salazar et al. Food Hydrocolloids 122 (2022) 107048

Fig. 2. Micrographs of banana flour with 546x magnification. A: Banana pulp with sodium metabisulfite (PF-preT); B: Banana pulp, without sodium metabisulfite
(PF-unT); C: Whole Banana, with sodium metabisulfite (WF-preT); D: Whole Banana, without sodium metabisulfite (WF-unT).

diameter). The particle size measured according to their long diameter (Fig. 2), showing that the drying process did not affect the internal
indicates that a high percentage of particles are between 40 and 50 μm, composition. A variety of structures in a similar or slightly smaller size
especially in pretreated whole banana flours (P < 0.05), while in un­ range were observed in whole banana flour from Musa acumminata and
treated whole banana flours, the highest percentage of particles measure non-commercial varieties from South Africa, pretreated with various
20–30 μm (Table 2). The particle sizes were consistent with those re­ solutions of organic acids (Anyasi et al., 2017), and in banana (Musa spp.
ported in three cultivars of Colombian Musaceae banana pulp starch AAA variety Mountain from India) pulp flour pretreated with hot water
treated with sodium bisulfite (3 g/L) (Chávez-Salazar et al., 2017), in and 1% citric acid, Ahmed et al. (2020) found particles measuring
banana (Musa acuminata AAA) pulp flour without further treatment also 3.47–52.3 μm (lyophilized) and 14.5–62.8 μm (dried in oven).
from Colombia (Aguirre & Castaño, 2015), and in banana (Musa para­
disiaca L) pulp starch treated with (NaOCl, 3%) from Mexico (García-­ 3.2.5. Differential scanning calorimetry (DSC)
Tejeda et al., 2011). The starch granules maintained their integrity The DSC analysis is shown in Table 3. The results showed a slightly
lower gelatinization temperature range (To-Tc) for untreated pulp flour,
while the highest melting point (Tm) was observed in the pretreated
Table 3
DSC results for pulp and whole banana flours.
whole banana flour (P < 0.05). An increase in the (Tc-To) range in­
dicates a high amount of granule modification in the crystalline and
Parameters PF-preT PF-unT WF-preT WF-unT
amorphous domains (Kong et al., 2012). The endothermic peaks for all
samples and phase transitions of the gels produced by the absorption or
b a
To ( C)

69.67 ± 0.47 71.75 ± 0.12 72.42 ± 71.75 ± 0.58a
0.59ab
removal of heat appeared at temperatures between 74 ◦ C and 78 ◦ C.
Tm (◦ C) 74.00 ± 0.01b 75.50 ± 0.71b 78.33 ± 0.47a 75.12 ± 0.07b
Tc (◦ C) 79.25 ± 0.82b 79.25 ± 0.82b 82.58 ± 0.13a 80.93 ±
Similar values of gelatinization temperature (74 and 77 ◦ C) were re­
0.11ab ported in Musa paradisiaca, var. Criollo and Macho, respectively (Bel­
ΔH (Jg− 1) 20.68 ± 0.99b 19.78 ± 17.80 ± 0.78c 32.23 ± 0.42a lo-Pérez et al., 2000). However, these ranges of temperature could
0.21bc depend on the starch type and the variety of bananas. Thus, in green
To: ‘onset’ initial temperature, Tm: ‘melting’ peak temperature, Tc: ‘conclusion’ banana (Musa cavendishii) flour from Brazil, Tribess et al. (2009)
or final temperature, ΔHgel: gelatinization enthalpy. PF-preT: Banana pulp flour observed that the peak temperature varied from 67.95 to 68.63 ◦ C and
with sodium metabisulfite; PF-unT: Banana pulp flour without sodium meta­ reported that the changes depend on the drying conditions of the flours.
bisulfite; WF-preT: Whole Banana flour, with sodium metabisulfite; WF-unT: According to Zhang et al. (2014), starch with amylose: amylopectin
Whole Banana flour, without sodium metabisulfite. Different letters (a, b, c, d) ratios 28:72 gelatinize in the range of 52–65 ◦ C, while starch with a high
indicate significant differences between samples.

7
D. Salazar et al. Food Hydrocolloids 122 (2022) 107048

amylose content (amylose: amylopectin ~70:30) gelatinized at higher


temperatures (~160–170 ◦ C).
The highest Tm value corresponds to the pretreated whole banana
flour (p < 0.05). Some authors reported that high Tm values could be
due to the higher content of starch and compounds such as proteins,
lipids, and fiber that are degraded at higher temperatures but that
require less energy consumption (ΔHgel) (Alcázar-Alay & Meireles,
2015; Polesi, 2009), although this fact was not observed in the present
work. Furthermore, a higher enthalpy value of gelatinization (ΔHgel)
was observed in the untreated whole banana flour (P < 0.05). In this
connection, Thys (2009) reported that when starch has a low amylose
content, the enthalpy variation value is higher. This fact could explain
the enthalpy value for WF-unT flour, which was the one with the lowest
percentage of amylose (13.28%). Despite this, PF-preT also obtained a
high enthalpy value having the highest amylose content (Table 1).
Ahmed et al. (2020) found values of gelatinization temperature (Tg) for
pulp flour dried in an oven at 55 ◦ C and pretreated with heat and citric
acid (1%) of 83.39 ◦ C, and indicated that the highest gelatinization
temperature (Tg) values according to treatments are related to its higher
protein and fiber content that compete and capture part of the available
water during starch gelatinization, increasing the endothermic transi­
tion T. As for the second thermal transition found (109.23 ◦ C) by these
authors, they related it to the starch-lipid complex. On the other hand,
the values for ΔH found by these authors for the first transition were
noticeably lower (12.5 J/g) that those found in the present work for any
flour. Lower enthalpy values are related to lower amylose contents in
starches from several vegetables (Hernández-Medina et al., 2008), but
this fact was not observed in the present work.

3.2.6. Swelling power and solubility


The swelling power (SP) and solubility (S) are shown in Fig. 3 A-B,
respectively. The results were related to temperature, showing a marked
increase from 70 ◦ C. Both parameters showed the degree of interaction
between the starch chains inside the amorphous and crystalline domains
of the granules. This interaction is affected by the amylose: amylopectin
ratio and by the bond distribution and molecular weight characteristics
of both amylose and amylopectin (Zhang et al., 2005). The swelling of
starch by a heat treatment is related with the amylopectin content, while
amylose is a diluter and inhibits swelling (Lii et al., 1996), although in
flours, the swelling could be associated with starch and other com­
pounds that also compete for water. In the present work, samples
showed low values at temperatures below 70 ◦ C for both parameters,
while at 80 ◦ C these properties increased with temperature (Table 3).
This fact could be due to the breaking of hydrogen bonds; water mole­
cules bind to the hydroxyl groups released, the granules expand and
amylose is exuded (de Assis et al., 2009) to be then suspended in water,
together with other non-starch-containing components during heat and
centrifugation treatments (Marta et al., 2019). Torres et al. (2005)
observed a significant degradation of starch granules occurring at a
higher temperature (80 ◦ C), contributing to increased solubility. In the
present work, the swelling behavior expressed as g of gel/g of soluble
solids (Fig. 3A) presented a similar profile in all flours, indicating that
differences in starch, amylopectin and amylose contents in the samples
do not seem to be as determinant as the presence of the peel in the flours,
since whole banana flours showed a slightly higher swelling power than
pulp flours.
A similar behavior was observed in banana Cavendish (Musa acu­ Fig. 3. (A) Swelling power, (B) Solubility and (C) Water absorption capacity
minata from Brazil) flours with and without the peel, with a swelling (WAC) of flours as a function of the temperature (50–80 ◦ C). PF-preT: Banana
power of 6.31 g/g of soluble solids and 5.74 g/g of soluble solids, pulp flour with sodium metabisulfite; PF-unT: Banana pulp flour without so­
dium metabisulfite; WF-preT: Whole Banana flour with sodium metabisulfite;
respectively but at lower temperatures (70 ◦ C), (Bezerra et al., 2013).
WF-unT: Whole Banana flour without sodium metabisulfite. Different letters (a,
The temperature in this study did not exceed 80 ◦ C on account of the
b, c …) indicate significant differences between samples at same temperature
altitude (2520 a.m.s.l.) at which the tests were carried out, considering and different letters (x, y, z …) indicate significant differences between tem­
the boiling temperature is around 89.8 ◦ C, in contrast with Bezerra et al. peratures of the same sample.
(2013) who reached temperatures up to 90 ◦ C in their study. These
authors also reported solubility values in banana flour of 5.36 g/g of
soluble solids (with the peel) and 4.48 g/g of soluble solids (without the

8
D. Salazar et al. Food Hydrocolloids 122 (2022) 107048

peel) at 70 ◦ C; in ripe Cavendish banana flour, solubility increased 15% must be considered in order to choose the most suitable suspension
when temperature was augmented from 55 ◦ C to 95 ◦ C (Ng et al., 2014), conditions. For instance, to obtain a very thin coating, the suspension
or 10% at 92.5 ◦ C in banana pulp flour (Musa spp) from Indonesian crops should be very low in viscosity and vice versa. In the case of films,
(Marta et al., 2019). With respect to the use of metabisulfite, it was whether the processing is by casting or by extrusion will have to be
observed that the solubility was slightly lower in pretreated samples, but considered (casting requires conditions that avoid the formation of
the differences were not significant at all temperatures; the same fact bubbles and therefore, a solution that is not very viscous, however, the
was observed for the swelling power (P < 0.05). These results are in extrusion method requires a very viscous pellet).
accordance with the study of Paterson et al. (1994) in corn, potato, 3.3.2.1.1. Flow curve. The flow curves of filmogenic suspension are
wheat, rice cassava, and sago starches. In this connection, Anyasi et al. shown in Fig. 4 A-B. The shear strength and the viscosity results revealed
(2017) did not observe differences in the swelling of unripe banana flour a pseudoplastic behavior of the banana flours, typical of non-Newtonian
(Musa species) treated with organic acids (ascorbic, citric, and lactic fluids, since the viscosity was inversely proportional to the shear
acids) before drying. These authors added that heat-moisture treatment, strength (Chhabra, 2010, pp. 3–34; Sívoli et al., 2012) with a shear
rather than the organic acid pretreatment of the flours, contributed to thinning behavior. The structural collapse of the molecules owing to the
differences in the gelatinization and transition temperatures. hydrodynamic effect of the forces generated would explain this
behavior. Whole banana flours presented a similar behavior for viscos­
3.2.7. Water absorption capacity (WAC) ity; however, pretreated pulp flour showed higher viscosity than the
Fig. 3 C shows the results of the WAC as a function of temperature. In untreated one. PF-preT had the highest viscosity values, coinciding with
almost all cases, the WAC slightly increased as the temperature a high content in amylopectin, while the lowest viscosity values corre­
increased ≈7% until reaching 80 ◦ C. These values are similar to those sponded to PF-unT, in which the amylopectin content was lower and
obtained for green bananas (Musa spp. AAA) ‘Mountain’ variety from therefore, could produce a weak reinforcement of the network (Her­
India at 25 and 70 ◦ C (Ahmed et al., 2020). At 80 ◦ C, starch gelatini­ nandez-Perez et al., 2021). This behavior could also be attributable to
zation occurs, and WAC noticeably increases (Pratiwi et al., 2018); the presence of metabisulfite, since this compound is a reducing agent
moreover, denatured proteins, fiber such as hemicelluloses, and poly­ that could increase water absorption, forming a more stable gel
saccharides such as pectins, can also contribute to rise the WAC at 80 ◦ C (Rajabzadeh & Asadian, 2006).
(Alkarkhi et al., 2011). Whole banana flours (pre and untreated) showed The shear strength increased with shear rate in all samples. The flow
slightly higher WAC than pulp flours (P < 0.05), probably owing to the profiles showed a nonlinear relationship between the shear strength and
greater number of hydroxyl groups found in the fiber structure, which shear rate, which is characteristic of a non-Newtonian behavior. The
tends to allow more water interactions through hydrogen bonding shear strength and viscosity were lower in the untreated pulp flour
(Aziah et al., 2012; Rosell et al., 2001). The chemical composition of the suspension compared with the other samples. The decrease in viscosity
flours could influence the WAC; protein participates in a competition for with shear rate could be attributed to the breaking of the entanglement
water with starch because at 80 ◦ C, proteins form a network that pre­ between the chains of the polymeric matrix, which induces a more
vents the diffusion of water into the starch granules, thus limiting random orientation of the molecules; so that the interactions between
swelling (Agama-Acevedo et al., 2009; Rodríguez-Ambriz et al., 2008; adjacent chains are reduced, giving a decrease in viscosity (Wang et al.,
Traynham, 2006). 2015). Bertolini et al. (2010) reported that flours from banana (Musa
acuminata Colla var. Nanicão form Brazil) pulp showed higher viscosity
values in contrast with those from the peel, probably due to their higher
3.3. Characterization of flours filmogenic suspensions starch and lower fiber contents. These authors observed that the pres­
ence of citric acid in the pretreated flours showed higher viscosity values
3.3.1. Density and pH than the control (non-treated), suggesting that the acid could modify the
Density values in filmogenic suspensions range from 1.024 to 1.031 starch granules, resulting in the formation of a more consistent and
g/cm3 (Table 4). Density is influenced by the chemical composition, stronger network similar to that of cross-linked starch.
mainly by fiber, since it alters the compaction of the polymer matrix; for The rheological adjustment results are shown in Table 5. Except for
example, when it is added, glycerol tends to decrease the dispersion. the untreated whole banana flour, the Ostwald de Waele model presents
However, in the present work, neither the presence of the peel nor the the best correlation adjustment for the flour suspensions. This is because
effect of metabisulfite had an effect on density (P > 0.05). The pH was the power-law allows describing many fluids containing soluble solids
between 5.35 and 5.80 (P < 0.05), and a slight drop was observed in the with high molecular weight (Aprianita, 2009). The other rheological
treated flours compared with the untreated ones. These values were models applied in this study (i.e. Newtonian and Casson) had a lower
similar to those reported by Borges et al. (2009) in suspensions of green adjustment of the data according to the determination coefficient (R)
pulp banana flour (Musa spp.) from Brazil. and thus were discarded. Based on the Ostwald de Waele model, the flow
behavior index (n) values ranged from 0.31 to 0.41, indicating a
3.3.2. Rheological characterization non-Newtonian behavior and showing the fluid’s pseudoplasticity de­
gree. This work showed that the suspension analyzed presented a
3.3.2.1. Rotational viscoelastic properties. The rheological behavior of pseudoplastic behavior (pseudoplasticity occurs when n is less than 1,
flour suspensions provides insight into their ability to form coatings and and the greater the difference relative to the unit, the greater the
films on an industrial scale. In addition, the type of industrial processing pseudoplasticity of the product). As for the consistency index (K), the
values ranged from 3.31 to 5.13, being higher in untreated whole ba­
Table 4 nana and pretreated pulp flours (Table 5). The untreated whole banana
Density and pH values of the filmogenic suspensions. flour suspension was adjusted to the Herschel Bulkley model, consid­
PF-preT PF-unT WF-preT WF-unT ering it presented the best coefficient of determination (R); in this
Density (g/ 1.031 ± 1.028 ± 1.024 ± 1.029 ±
sample, an effort threshold (τ0) of 1.79 was calculated. This sample
cm3) 0.003a 0.003a 0.000a 0.004a behaved as solids under low stress and liquids under high stress, so the
pH 5.54 ± 0.04a 5.71 ± 0.01b 5.35 ± 0.02c 5.80 ± 0.01d real flow is only noticeable above a specific threshold value (Malkin &
PF-preT: Banana pulp flour with sodium metabisulfite; PF-unT: Banana pulp Isayev, 2017). The presence of fiber influences the rheological charac­
flour without sodium metabisulfite; WF-preT: Whole Banana flour, with sodium teristics of the fluid. Bertolini et al. (2010) observed lower viscosity
metabisulfite; WF-unT: Whole Banana flour, without sodium metabisulfite. values in the flour suspensions from banana peel (Musa acuminata Colla
Different letters (a, b, c, d) indicate significant differences between samples. var. Nanicão from Brazil) than those obtained in the present study. This

9
D. Salazar et al. Food Hydrocolloids 122 (2022) 107048

Fig. 4. Steady shear rheological properties


of filmogenic suspensions. A) Shear strength
(Pa) vs. shear rate (1/s). B) Viscosity (m Pa s)
vs. shear rate (1/s). C) Viscosity ratio (mPas)
as a function of up (20–90 ◦ C) temperatures.
D) Viscosity ratio (mPas) as a function of
down (90-20 ◦ C). E) Viscosity values at
20 ◦ C, 90 ◦ C, after cooling to 20 ◦ C and % of
recovery viscosity after cooling at 20 ◦ C. PF-
preT: Banana pulp flour with sodium meta­
bisulfite; PF-unT: Banana pulp flour without
sodium metabisulfite; WF-preT: Whole Ba­
nana flour with sodium metabisulfite; WF-
unT: Whole Banana flour without sodium
metabisulfite.

pumping systems and evaluate the behavior of flour suspensions when


Table 5
used as ingredients in fluid foods, such as ketchup, mustard, and other
Rheological parameters and adjustment to mathematical models. Where K:
types of sauces.
consistency index, n: power low index, R: determination coefficient.
3.3.2.1.2. Effect of temperature on filmogenic suspensions. Fig. 4C–E
Rheological SAMPLES
shows the relationship of viscosity as a function of temperature of fil­
Model
PF-preT PF-unT WF-preT WF-unT mogenic suspensions. At 20 ◦ C the values are very different among the
Ostwald de K 4.49 ± 3.31 ± 3.33 ± 5.13 ± batches. The initial viscosity is higher in the filmogenic dispersions of
Waele: 0.15b 0.38c 0.20c 0.18a pretreated pulp flour, which coincides with a higher amount of starch.
τ = k γn n 0.41 ± 0.36 ± 0.39 ± 0.31 ± López et al. (2015) observed a decrease on viscosity when plasticizer
0.01a 0.01b 0.01a 0.01c
(glycerol) was added in a film-forming suspension of ahipa, cassava and
R 0.997 0.9909 0.9999 0.9794
Herchey-Bucley: τ0 1.91 ± 1.72 ± 1.77 ± 1.79 ± corn starch, but in the present study all flour suspensions contain the
τ = τ0 + k(γ)n 0.01a 0.06b 0.01b 0.01b same quantity of plasticizer.
K 4.49 ± 3.31 ± 3.33 ± 5.13 ± As the temperature of the suspensions increased, the viscosity of the
0.15b 0.38c 0.20c 0.18a flour suspensions dropped considerably. This behavior was similar in all
n 0.41 ± 0.36 ± 0.39 ± 0.31 ±
0.00a 0.01b 0.01a 0.01c
samples; however, in WF-preT, viscosity was lower as compared with
R 0.9914 0.9632 0.9831 0.9876 the other samples. Likewise, it is observed that the drop in viscosity as a
function of the increasing temperature in the pretreated samples was
PF-preT: Banana pulp flour with sodium metabisulfite; PF-unT: Banana pulp
more pronounced, exhibiting a higher slope than the corresponding
flour without sodium metabisulfite; WF-preT: Whole Banana flour, with sodium
metabisulfite; WF-unT: Whole Banana flour, without sodium metabisulfite.
untreated samples, and additionally presenting a higher amylose con­
Different letters (a, b, c, d) indicate significant differences between samples. tent. The starch granules break in the suspension during heating; thus,
the most soluble amylose leaches out from the broken starch granules,
causing a reduction in viscosity. In both pulp samples at the end of the
type of fluid is less thick when subjected to high deformation rates than
heating ramp, viscosity was quite similar; however, this behavior was
when sheared slowly, resulting in less resistance to flow due to the
not observed in whole banana flours (Fig. 4C). Bertolini et al. (2010)
presence of high molecular weight substances. The properties of this
found that banana peel flour high in fiber content showed lower
fluid make it possible to establish and calculate the transport and

10
D. Salazar et al. Food Hydrocolloids 122 (2022) 107048

viscosity during heating, which is attributed to fiber competing with period of constant high temperature (at 95 ◦ C) and mechanical shear
starch for water. The molecular distances increase due to the decline in stress, a viscosity breakdown occurs due to the presence of more soluble
intermolecular forces with increasing temperature, so that suspensions amylose, while in the suspensions that were cooled down, viscosity
can flow more efficiently, resulting in a decrease in particle-particle increased as a result of the re-association of the starch molecules to form
interactions (Bertolini et al., 2010). The loss of viscosity eventually a gel network.
depends on temperature, the shear stress applied to the system and the
nature of the starch (Díaz Ocampo, 2018). 3.3.2.2. Dynamic viscoelastic properties
As temperature drops and cools (Fig. 4 D), showing an inverse 3.3.2.2.1. Sweep amplitude. The behavior of the storage modulus
relationship, starch molecules re-associate to form a firm gel network, (G′ ) and loss modulus (G′′ ) as a function of strain (%) are shown in Fig. 5
which leads to an increase in viscosity, although only the untreated A-B. The filmogenic suspensions showed significant differences due to
batches (PF-unT and WF-unT) reached viscosity values similar to the the pretreatment with the antioxidant and to the presence of the peel (P
initial ones when temperature went down again to 20 ◦ C, with a 96.5% < 0.05), the lower values corresponding to PF-unT, the sample with the
and 92.87% of recovered viscosity respectively (Fig. 4 D). Since the lowest content in amylopectin, which produces a weak reinforcement of
plasticizer is the same in all samples, it does not seem to affect the re­ the network (Hernandez-Perez et al., 2021). At a low strain range, the
covery capacity of viscosity when the temperature decreased again. The results indicated that the storage modulus G′ is greater than the loss
worst recovery capacity of viscosity in the filmogenic dispersions modulus G′′ , showing that the material is highly structured, and
occurred in the pretreated samples, corresponding with a greater implying a well-organized gel-like behavior (Rosalina & Bhattacharya,
amount of amylose (Fig. 4 E). In addition, WF-preT presented an even 2002). After 1% strain, G′ tends to decrease and a curve is observed,
worse recovery, which may be favored by the presence of other com­ which is defined as the limit value of the viscoelasticity region. How­
pounds as fiber and protein. The effect of amylose during cooling is one ever, the untreated pulp flour filmogenic suspension showed a behavior
of the initial causes of the firmness of the gel, which later would become in which the elastic and viscous modules presented similar low values
increasingly firmer due to the progressive crystallization of amylopectin (Fig7 A–B). This fact would indicate that the filmogenic suspension is in
and co-crystallization of amylose together with amylopectin within the the boundary between a viscous liquid and a gel, so the critical strain is
granules (Biliaderis, 1991; Glorio Paulet et al., 2009) in the retrogra­ lower in the other samples. At a higher strain, the energy is dissipated in
dation. In this connection, Ng et al. (2014) reported that in ripe Cav­ the system and the suspension tends to exhibit a fluid-like behavior
endish banana (from Malaysia) composite suspensions subjected to a (Clark & Ross-Murphy, 1987, pp. 57–192; Lapasin, 2012). Pretreated

Fig. 5. Dynamic rheological properties of


filmogenic suspensions. A) Storage modulus
(G′ , Pa) vs. deformation (%). B) Loss
modulus (G′′ , Pa) vs. deformation (%). C)
Dependence of loss modulus (G′′ , Pa) with
the frequency (Hz). E) Loss factor tg δ vs.
strain. D) Dependence of storage modulus
(G’; Pa) with the frequency (Hz). E) Depen­
dence of loss modulus (G′′ , Pa) with the
frequency (Hz). E) Loss factor tg δ vs. strain.
PF-preT: Banana pulp flour with sodium
metabisulfite; PF-unT: Banana pulp flour
without sodium metabisulfite; WF-preT:
Whole Banana flour with sodium meta­
bisulfite; WF-unT: Whole Banana flour
without sodium metabisulfite.

11
D. Salazar et al. Food Hydrocolloids 122 (2022) 107048

pulp flour may show a similar behavior to that of whole banana flours in Supervision, Validation, Writing – review & editing, Visualization.
the filmogenic dispersion owing to the amylopectin content (Table 1),
which enhances the rigidity of the material and is reflected in higher Acknowledgments
values for the moduli. Even though G’’> G’ at large strain is only slightly
higher, the tangent δ never reaches values greater than two (Fig. 5 C), The authors are grateful to Dirección de Investigación y Desarrollo
which is indicative of the fact that the elastic component predominates (DIDE) and the Technical University of Ambato-Ecuador for financial
in all the samples for all the exerted strain. support Resolution 1313-CU-P-2015, Project PFCIAL17 “Development
3.3.2.2.2. Frequency sweep. The viscoelasticity of the storage (G′ ) of active biodegradable films from rejection banana flour (Musa genus)
and loss (G′′ ) moduli increased as a function of frequency (Hz) (Fig. 5D and its application”; Projects NANOALIVAL AGL 2017-84161 funded by
and E). In pretreated pulp and whole banana flours, G′ and G′′ increased MICINN, Spain and European Regional Development Fund (FEDER), and
with frequency for larger storage moduli. These results could indicate project 202070E218 funded by CSIC, Spain.
that filmogenic suspensions form strong gels according to amylopectin
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