agronomy

Article
Characterization and Technological Potential of Underutilized
Ancestral Andean Crop Flours from Ecuador
Diego Salazar 1,2, * , Mirari Arancibia 1 , Iván Ocaña 1 , Roman Rodríguez-Maecker 3 , Mauricio Bedón 4 ,
María Elvira López-Caballero 5 and María Pilar Montero 5, *

1 Facultad de Ciencia e Ingeniería en Alimentos, Universidad Técnica de Ambato, Av. Los Chasquis y Rio
Payamino, Ambato 180206, Ecuador; [email protected] (M.A.); [email protected] (I.O.)
2 Facultad de Veterinaria, Universidad Complutense de Madrid, 28040 Madrid, Spain
3 Departamento de Energía y Mecánica, Carrera de Petroquímica, Universidad de las Fuerzas Armadas—ESPE,
Latacunga 050105, Ecuador; [email protected]
4 Escuela Superior de Ingeniería y Tecnología, Universidad Internacional de la Rioja, 26006 Logroño, Spain;
[email protected]
5 Instituto de Ciencia y Tecnología de Alimentos y Nutrición (ICTAN-CSIC), Calle José Antonio Novais 10,
28040 Madrid, Spain; [email protected]
* Correspondence: [email protected] (D.S.); [email protected] (M.P.M.)

Abstract: Ancestral Andean crop flours (ACF) from Ecuador such as camote (Ipomea Batatas), oca
(Oxalis tuberosa), achira (Canna indica), mashua (Tropaeolum tuberosum), white arracacha (Arracacia



xanthorrhiza), taro (Colocasia esculenta) and tarwi (Lupinus mutabilis sweet) were characterized in terms

 of physico-chemical and techno-functional properties in order to identify their potential as new
Citation: Salazar, D.; Arancibia, M.; alternative ingredients in food products. Flour from camote, oca, achira and arracacha showed a low
Ocaña, I.; Rodríguez-Maecker, R.; protein content (<5%), mashua and taro had ~9% and tarwi flour registered higher values than 52%.
Bedón, M.; López-Caballero, M.E.; Carbohydrate content ranged from 56–77%, with the exception of tarwi, just reaching 6.9%. Starch
Montero, M.P. Characterization and content was relatively low in ACF but in taro and tarwi, starch practically constituted almost all the
Technological Potential of carbohydrates. The highest amylose content in starch, in decreasing order, was found in mashua,
Underutilized Ancestral Andean oca, tarwi and achira flours, the rest being ≤15%. Fiber content exceeded 10% in most crops, except
Crop Flours from Ecuador. Agronomy
for oca flour with 5.33%. Fat content was generally lower than 1%, except in tarwi with ~17%. All
2021, 11, 1693. https://doi.org/
flours showed a gel-like behavior G0 > G00 , this being very similar in camote, achira and tarwi flours.
10.3390/agronomy11091693
The exception was taro with G0 < G00 . Mashua flour registered the highest value for phenol content
Academic Editors: Marten Sørensen
(60.8 µg gallic acid equivalents/g of sample); the content of phenols was not exclusively responsible
and Carla Gentile for the antioxidant activity, since flours with the highest activity were arracacha and tarwi, which
presented the lowest phenol content among all flours. Principal component analyses (PCA) showed
Received: 27 July 2021 a high correlation between moisture, fiber, solubility and water absorption capacity, with viscoelastic
Accepted: 23 August 2021 behavior and total phenolic content; while starch content was correlated with melting temperature,
Published: 25 August 2021 poorly and inversely related to protein and fat. For PC1, achira, camote and taro flours were very
similar, and different from oca and mashua flours. Tarwi showed its own characteristics according to
Publisher’s Note: MDPI stays neutral PC1 and 2. Because of their properties, Andean crop flours could have a great potential for use in
with regard to jurisdictional claims in food technology.
published maps and institutional affil-
iations. Keywords: andean crop flours; physico-chemical characteristic; morphology; functional proper-
ties; antioxidant

Copyright: © 2021 by the authors.

Licensee MDPI, Basel, Switzerland. 1. Introduction
This article is an open access article
The Andean region comprising Bolivia, Peru, Ecuador and Colombia has been cat-
distributed under the terms and
alogued as one of the areas of the world possessing the greatest plant richness and crop
conditions of the Creative Commons
diversity with an important collection of germplasm related to three of the main tubers
Attribution (CC BY) license (https://
that are the most typically consumed: oca (Oxalis tuberosa), mashua (Tropaeolum tuberosum)
creativecommons.org/licenses/by/
and melloco (Ucullus tuberosus) [1,2]. Andean crops are developed in areas considered
4.0/).

Agronomy 2021, 11, 1693. https://doi.org/10.3390/agronomy11091693 https://www.mdpi.com/journal/agronomy

Agronomy 2021, 11, 1693 2 of 28

by modern agriculture (mainly focused on extensive crops) as marginal lands, even with
a reduced probability of producing quality food; however, adapting to the environment
makes the growth of these crops possible [2]. The richness of these crops in nutrients and
pharmacological properties [3,4], as well as their use in traditional medicine have been
previously described. The exploitation of extensive crops by large companies, it being
economically more profitable to produce and market a few plant species such as potato,
rice, soya or corn, make Andean crops underutilized or in disuse, limited to domestic
consumption in certain restricted regions, so that the reduced consumption will be less
each day.
Consumers are increasingly demanding both raw materials and intermediate or final
products with better and varied nutritional characteristics perceived as natural [5] and, if
possible, that contribute to their health and wellbeing [6]. In this sense, tubers, rhizomes
and legumes from the Andean region, due to their high nutritional value, could play
an important role in the development of food products, even functional products, as well
as covering the demand of food for people with special requirements, as it is the case of
those intolerant or allergic to gluten, since some Andean crops are gluten-free. In addition,
the promotion of the exploitation of these resources would be of socio-economic interest,
favoring biodiversity and the impact and sustainability of the Andean region.
There are several studies in the literature on these crops, not only from the Andean
region, but also from other geographical areas. It is well known that their composition can
vary due to factors inherent to the crop, and also greatly by the geographical distribution
of the cultivars, as they are conditioned by climatic factors and the type of soil [7–9],
sometimes giving rise to denominations of origin [10,11]. In the Andean region, differences
of thousands of meters can be found within the higher areas (“altiplanos”), and even more
so with those near sea level; therefore, the climatic conditions can be very different. In
this sense, Sulistiani, et al. [12] recently studied the effect that different geographical areas
could have on the biochemical parameters of camote in Indonesia, taking into account
temperatures and fertilizers, and observing the greatest differences between highlands and
lowlands, being the variations in altitude of 1400 m between them.
The knowledge of the nutritional composition and physico-chemical properties of
crops according to regions and other factors, is of great importance to evaluate their
functional properties and technological suitability. Obtaining flours is a trigger for the
sustainable search and production of these non-conventional crops. These flours may
or may not have similar properties to traditional flours, so Andean crop flours can be
an alternative option to substitute traditional flours in the industry, considering as well
their possible different applications. Most studies have referred to tubers or grains, or their
starch, such as arracacha flour from Brazil [7], taro flour from Cuba [13], starch and flour of
Brazilian camote [14], flour of the Philippines camote [15], flour and starch of taro from
Thailand varieties [9] and Tarwi flour from Egypt [16]. However, there are few studies on
the characterization of flours of some of these crops from the Andean region.
The objective of the present work is to obtain flours from Andean crops of different
nature (5 tubers, 1 rhizome and 1 legume grain), selected for being the most consumed in the
rural areas in the region of Ambato (Ecuador). Then, the physico-chemical characterization
and techno-functional properties of these flours were analyzed to identify their potential as
new ingredients in the development and production of healthier foods.

2. Materials and Methods

2.1. Andean Crop Flours
Andean crops ready for consumption were purchased in a market in Ambato, Tun-
gurahua (Ecuador) grown at an altitude of 2500 m above sea level (masl). According to
their botanical nature, Andean crops were classified into three categories: (A) rhizomes:
achira (Canna indica); (B) tubers: camote (Ipomoea batatas), mashua (Tropaeolum tuberosum),
oca (Oxalis tuberosa), taro (Colocasia esculenta), and white arracacha (Arracacia xanthorrhiza);
C) legume grain: tarwi (Lupinus mutabilis sweet). To obtain the flours, the tubers, rhizomes
Agronomy 2021, 11, 1693 3 of 28

and grains were washed with water and brushed until all the impurities found in the
surface were eliminated. Then, tubers and rhizomes were cut into slices of ~3 mm and
tarwi was used in its original form. All slices and grains were dried at 60 ◦ C for ~6 h in
a convective oven dryer (Gander MTN, Saint Paul, MN, USA) until the moisture values
were constant. Finally, the dried slices of the Andean crops were milled in an industrial
mill for grains (Inox equipment IE1, Riobamba, Ecuador), the grinding was carried out
through the crushing process until obtaining a fine powder. All samples were hermetically
packed and stored at room temperature until further analysis.

2.2. Proximate Composition of Flours and Energy Value

The moisture, ash, crude protein, crude fiber, and fat contents were evaluated follow-
ing the official methods AOAC 925.09, AOAC 923.03, AOAC 920.87, AOAC 985.29, and
AOAC 922.06, respectively (AOAC, 2005) [17]. Carbohydrate content was determined by
difference. The analyses were performed in triplicate.
The total calorie content was estimated x100 g, as the overall sum of calories of the
individual components, taking into account that the energy value for each component
is as follows: fat (×9 kcal/g), protein (×4 kcal/g), carbohydrate (×4 kcal/g), and fiber
(×2 kcal/g) (FAO, 1988) [18], and expressed as kcal/100 g. Values were estimated by the
Atwater system.

2.3. Total Starch and Amylose Content

Total starch was quantified enzymatically (AOAC Method 996.1, AACC Method 76-13.01)
using a Megazyme Total Starch Assay Kit (Megazyme). The amylose content were quan-
tified with Amylose/Amylopectin Megazyme Assay Kit (Megazyme). The absorbance
measurements for the determination of the starch and amylose contents were carried out
using a UV-Vis spectrophotometer (Thermo Fisher, Waltham, MA, USA) at a wavelength
of 510 nm. All determinations were carried out in triplicate.

2.4. Physico-Chemical Properties of Flours

2.4.1. pH and Titratable Acidity
The determination of pH and acidity were carried out following the method of
Salazar, et al. [19]. All tests were carried out in triplicate.

2.4.2. Color
In order to measure the color of flours, a colorimeter (ColorFlex EZ, HunterLab, Reston,
VA, USA) and the CIELAB color scale were employed, following the method described
by Salazar, et al. [20]. The flour samples were placed in small Petri dishes at a depth of
0.5 cm to obtain a uniform distribution. Measurements were made in five sections of the
box. A minimum of 25 measurements were made in different parts of the sample at least
in triplicate.

2.4.3. Granulometry
The particle size was determined according to the Standard INEN NTE 0517 (1981), as
described by Salazar, et al. [20]. Briefly, the method consisted of placing the flour (100 g) in
a set of 5 sieves (Tyler series, Mentor, OH, USA); the diameter decreased downward, and
the sieves were labeled starting from the top down 40 (420 µm), 60 (250 µm), 100 (149 µm),
140 (106 µm), 200 (75 µm) and the pan collector. The sieves vibrated mechanically in
a shaker equipment (Tyler series, Mentor, OH, USA) for 5 min and the flour retained in
each sieve, after being carefully collected, was weighed. To measure size, uniformity
index (UI) and fineness modulus (FM) were used. The fineness modulus is defined as
the sum of weight of the fractions retained in each sieve divided by 100; each weight of
fraction retained is multiplied by a factor number of the respective sieve (sieve 40: factor 5,
sieve 60: factor 4, sieve 100; factor 3, sieve 140: factor 2, sieve 200: factor 1, pan collecter:
factor 0). Fineness modulus of flours is classified in three categories: Fine (0–2), Medium
Agronomy 2021, 11, 1693 4 of 28

(2–4), and Coarse (above 4). The uniformity index classifies the particle size of flours into
fine, medium and coarse, and is expressed as g/10 g of sample of different particle size,
calculated by the average retention on the different sieves. The assays were undertaken
in triplicate.

2.4.4. Bulk Density

The bulk density (bD) of flours was determined as described by Gujska, et al. [21].
Inside a graduate cylinder, flour was added until the 100 mL line and weighed. The
bottom of the cylinder was gently tapped three times until there was no further diminution.
The bulk density was calculated by dividing the mass of the flours (g) by the volume
(cm3 ) occupied in the cylinder. The volume of the flours was used in mass/volume
calculation [22]. The determinations were carried out in triplicate.

2.4.5. Scanning Electron Microscopic (SEM)

The morphology of the flour samples was obtained with a scanning electron micro-
scope (SEM) (Tescan, Vega3, Warrendale, PA, USA). The organic samples were placed on
an aluminum support provided with a double-sided carbon tape, and each sample was
observed at 3 Kv in the microscope, with a field of view of 253 µm and a magnification
of 546×. The individual particle size distribution was determined using the software of
the equipment by measuring the minor and major axis of the particles, and calculating the
mean value of all measurements by distribution ranges (0–10 µm, 10–20 µm, 20–30 µm,
30–40 µm, 40–50 µm and 50–60 µm). The distribution of the aggregates (considered as
several particles joined together) was determined in the same way. The total average
particle size was also determined. The results were expressed as the mean value.

2.4.6. Differential Scanning Calorimetry

Differential scanning calorimetry (DSC) measurements were taken with DSC 3 equip-
ment (Mettler Toledo, Columbus, OH, USA) and the analyses were carried out as described
by Salazar, et al. [20]. Approximately 10 mg each flour (dry weight basis), was weighed into
aluminum pan and 55 µL of distilled water was then added. An empty pan was used for
control purposes. The cups were hermetically sealed and held for 24 h at 4 ◦ C [23]. Finally,
the sample was placed inside the DSC equipment and heated from 30 to 120 ◦ C at a heating
rate of 10 K min−1 [24]. Nitrogen was used as a purge gas at a rate of 50 mL min−1 . The
tests were carried out in triplicate.

2.4.7. Swelling Power and Solubility

Solubility and swelling measurements were carried out according to the methodology
described by Andrade-Mahecha, et al. [7] with slight modifications. A suspension of 1% of
flour in water (w/v) was prepared and conditioned in a thermal bath at different tempera-
tures: 50, 60, 70, and 80 ◦ C for 30 min with constant agitation, and finally centrifuged at
4865× g for 15 min. The supernatant was separated, dried at 100 ◦ C to constant weight (solu-
ble solids weight), and the precipitate was the sediment or gel formed. Equations (1) and (2)
were used for determination. The analyses were performed in triplicate.

gel weight (g)

Swelling power = × 100% (1)
sample weight (g) − soluble solids weight (g)
 
soluble solids weight (g)
Solubility = × 100 (2)
sample weight (g)

2.4.8. Water Absorption Capacity (WAC)

The water absorption capacity (WAC) of the flours was determined according to
Andrade-Mahecha, et al. [7]. A dispersion of flour (1% w/v) in water was prepared in
a 500 mL centrifuge bottle, heated in a thermal bath at different temperatures: 50, 60, 70,
and 80 ◦ C for 15 min under constant stirring, and then centrifuged (D-78532, Hettich® ,
Agronomy 2021, 11, 1693 5 of 28

Tuttlingen, Germany) at 157× g for 10 min. After decanting the supernatant, each bottle
was weighed, and WAC was expressed using Equation (3).
 
g of water adsorbed
WAC (%) = × 100 (3)
g sample

2.5. Rheological Properties

For rheological evaluation doughs were prepared with 35% of Andean crop flours
and 65% of water. The rheological tests were performed in a Compact Modular Rheometer
(Anton Paar MCR302, Graz, Austria) using a cone-plate PP 25 (gap = 1 mm) for oscillatory
tests. All tests were developed at a controlled temperature (25 ◦ C). The viscoelastic behavior
of the suspensions was carried out using dynamic mode tests, by deformation sweeps at
a frequency of 1 Hz, and frequency scans in a range of 1–10 Hz. The registered dynamic
rheological parameters were: storage modulus (G0 ), and loss modulus (G00 ). The power law
model was used to fit both G0 (G0 = Go’·ωn’) and G00 = (G00 = Go”·ωn”) with the angular
frequency ω (1, 30, 60, and 90 rad/s). The tests were carried out at least in triplicate.

2.6. Total Phenolic Content and Antioxidant Activity

2.6.1. Total Phenolic Content
Total phenolic compounds were quantified using Folin-Ciocalteu reagent [25] with
certain modifications. For that, an aliquot of 2.5 mL of a flour in water suspension (250 mg
flour with 10 mL deionized water) was mixed with 1 mL of Folin-Ciocalteu reagent sample,
and samples were filtered prior the spectrophotometric analysis. The absorbance was
measured at 765 nm (Boeckel Co S-220). Gallic acid was used as a standard and the results
were expressed as µg gallic acid equivalent/g sample. All the samples were analyzed at
least in triplicate.

2.6.2. Antioxidant Activity

The antioxidant activity was determined using the ABTS free radical [2,20-azino-
bis-(3-ethylbenzothiazoline-6-sulfonic acid)] method using standard Trolox equivalent, as
described by Villacrés, et al. [26], with slight modifications. For that, 250 mg flour with
10 mL deionized water was prepared. Readings were made on a UV/V spectrophotometer
(Boeckel Co S-220, Hamburg, Germany) at a wavelength of 740 nm. The antioxidant activity
was expressed as Trolox eq./g sample (dry weight basis), and all samples were determined
at least in triplicate.

2.7. Experimental Design

Results were analyzed by one-way and two-way ANOVAs. Means were tested with
Tukey’s multiple comparison test, with a significance level α = 0.05 using GraphPad Prism
v5.03 (GraphPad Software, San Diego, CA, USA).
The multivariate analysis was carried out with all data values obtained from the flour
analyses. Correlations among properties and/or components were calculated. Factorial
analysis by principal component analysis was performed with varimax rotation. The
hierarchical cluster analysis method was used to explore the organization of samples in
groups depicting a hierarchy. The result of hierarchical cluster analysis is presented in
a dendrogram plot.

3. Results
3.1. Proximal Composition
The different proximal compositions of the Andean crops are shown in Table 1.
One fundamental parameter in farinaceous products is moisture content, as Barbosa, et al. [27]
mentioned, because it is implicated in the handling, storage and processing of farinaceous
foods, suggesting that it must be below 14% to maintain stability and avoid alteration. The
moisture values of flours ranged from 5.94% to 18.87%, mashua flour registering the highest
Agronomy 2021, 11, 1693 6 of 28

value followed by oca, probably attributed to the nature of the material. It is possible these
two flours had some other hygroscopic compounds. Thus, a substantial content of free
sugars (such as sucrose in oca), and hydrophilic proteins in mashua, could interact with
water through hydrophilic groups to establish hydrogen bonds, which would increase the
water presence in the samples [7,28].

Table 1. Chemical composition of andean crops flours: proximal composition, starch, amylose and amylopectin (%), calories
(kcal/100 g), and acidity (expressed as lactic acid percent).

Parameters Camote Oca Mashua Achira Arracacha Taro Tarwi

Moisture 6.20 ± 0.27 d 16.40 ± 0.18 b 18.87 ± 0.06 a 5.94 ± 0.12 d 6.16 ± 0.19 d 6.22 ± 0.26d 7.00 ± 0.03 c
Protein 4.65 ± 0.24 d 1.63 ± 0.07 e 9.12 ± 0.13 b 4.80 ± 0.15 d 2.10 ± 0.18 e 8.37 ± 0.14 c 52.82 ± 0.02 a
Fat 0.37 ± 0.06 b 1.06 ± 0.06 b 0.59 ± 0.07 b 0.63 ± 0.29 b 0.69 ± 0.08 b 0.73 ± 0.08 b 17.78 ± 0.64 a
Ash 3.24 ± 0.49 d 3.04 ± 0.24 d 4.94 ± 0.05 bc 8.04 ± 0.04 a 4.49 ± 0.18 c 5.55 ± 0.01 b 2.95 ± 0.07 d
Fiber 11.19 ± 0.11 d 5.33 ± 0.05 g 9.60 ± 0.05 e 11.51 ± 0.05 c 9.25 ± 0.02 f 14.90 ± 0.01 a 12.58 ± 0.01 b
Total CH 74.35 ± 0.36 b 72.54 ± 0.10 c 56.89 ± 0.25 f 69.09 ± 0.04 d 77.31 ± 0.45 a 64.23 ± 0.17 e 6.86 ± 0.60 g
Starch 40.05 ± 0.55 d 28.12 ± 0.39 e 22.21 ± 0.30 f 52.18 ± 0.72 b 42.82 ± 0.59 c 59.98 ± 0.82 a 5.90 ± 0.08 g
Amylose 6.23 ± 0.13 d 9.87 ± 0.36 b 9.68 ± 0.13 b 15.20 ± 0.22 a 4.49 ± 0.07 e 8.94 ± 0.08 c 1.95 ± 0.01 f
Amylopectin 33.82 ± 0.42 c 18.25 ± 0.03 d 12.53 ± 0.17 e 36.99 ± 0.50 b 38.33 ± 0.52 b 51.04 ± 0.74 a 3.95 ± 0.09 f
Calories 341.73 ± 1.65 b 316.88 ± 0.05 d 288.48 ± 0.98 e 324.18 ± 0.55 c 343.66 ± 0.01 b 326.77 ± 0.57 c 423.92 ± 0.49 a
pH 5.85 ± 0.01 e 6.35 ± 0.01 ab 5.88 ± 0.01 de 6.05 ± 0.01 c 6.29 ± 0.02 b 5.97 ± 0.01 cd 6.41 ± 0.09 a
Acidity 0.25 ± 0.01 e 0.24 ± 0.02 e 1.03 ± 0.03 a 0.50 ± 0.03 b 0.31 ± 0.01 d 0.43 ± 0.03 c 0.12 ± 0.01 f
Different letters (a, b, c . . . ) indicate significant differences between samples.

The flour protein contents comprised a wide range, from 1.63% (oca) to 52.82% (tarwi)
(p < 0.05) (Table 1). Again, the flour from tarwi (legume grain) shows a very different
composition, with a protein content similar to those reported by Villacrés, et al. [29] in
samples of debittered tarwi from Ecuador (54.05%), and much higher than that found in
tarwi flour from Egypt (43.17%) [16]. The higher protein content compared with the other
crops analyzed is due to its leguminous nature, with a high nitrogen fixation capacity [30].
A high protein content represents an alternative for the development of enriched foods with
a different source of protein or to balance protein-deficient flour blends, also conferring
texture to the flour. The protein contents in tuber and rhizome whole flours are similar to
those shown in mashua whole flour from Ecuador (9.21%) [31], or in achira extract from
Mysore, India (4.72%) [32]. However, the values of Andean crops in the present work were
lower to those found in camote pulp flour (6.3%) from Arequipa, Peru [33]; in Oca whole
flour (6.84%) [34]; in arracacha (6.27%) from Cajamarca-Colombia (2750 masl) [35], and Taro
(10.32%) from Cuba [13]. All of these variations could be attributable to the geographical
zones and also to the variety.
The fat content was quite low (<1.06%) in tuber and rhizome flours (Table 1), while
tarwi flour was the exception, with a fat content of 17.78%, as a consequence of the higher
amount of polyunsaturated fatty acids present in this legume (Oleic 40.40%, linoleic 37.10%,
linolenic 2.90%) [29]. The fat content in flours may differ depending on the crop variety and
the geographical area. Much higher values in a tuber than the ones found in the present
work were reported in achira extract grown on river banks in Mychuri, India (5.75%) [32].
However, the fat content was close to taro flours from Cuba (1.03%) despite their different
geographical location [13].
The ash content in Andean crop flours ranged from 2.95% to 8.04% (p < 0.05) (Table 1).
Achira flour obtained the highest values, almost similar to those reported by Andrade-
Mahecha, et al. [7] who documented 7.48% in achira flour from Conchal, Brazil, (591 masl).
The high ash value in achira is possibly due to the presence of minerals such as calcium,
potassium, phosphorus, and iron (2.85% ash) [36], since flours from Andean crops are
rich in mineral contents [37]. A high ash content was also found in taro flour from Cuba
(5.65%) [13].
Nowadays, it is desirable that foods have a significant fiber content due to the nutri-
tional properties that fiber may provide. Fiber content in these Andean flours ranged from
5.33% to 14.90%. In this sense, according to nutritional claims, the flours could be labeled
Agronomy 2021, 11, 1693 7 of 28

as “high fiber” food (at least 6 g of fiber per 100 g), due to the presence of pulp and peel.
Therefore, all of them would carry this nutritional claim, with the exception of oca flour,
which would only carry the nutritional claim of “source of fiber” (foods with at least 3 g of
fiber per 100 g) (Regulation 1924/2006) [38]. The peel is the part of the tubers, rhizomes
and seeds where compounds such as cellulose, hemicellulose, lignin and pectins could
be found [39]. Much higher values (25.1%) were found in achira extract from Mychuri,
India [32]. As for tarwi grains, the fiber content is similar to that found in taro flour from
Egypt [16]. Notably lower is the fiber content of taro flour from Cuba (4.38%) [13]; this
fact could be important, because the aforementioned flour would not hold the “high fiber”
claim as the one from Ecuador in the present work (14.90%).
Carbohydrate contents were significantly different in all flours (p < 0.05), and different
ranges were observed: from high (74–78% for camote and arracacha, respectively) to low
values (7%) in tarwi (Table 1). The results obtained in this work are similar to those reported
by Matsuguma, et al. [40] in white arracacha tuber (82.2%) from Brazil. On the other hand,
lower values (6.86%) in tarwi flour were observed in relation to those reported by Gross,
et al. [41] in tarwi flour (28.2%) from Chile. These variations may be related to genotypic
characteristics, metabolic status, environmental and maturity status [42]. Apart from tarwi,
lower CH contents corresponded to mashua and taro, which coincide with higher protein
contents in tubers. Legumes usually contain less carbohydrates than tubers, but in this
work, in tarwi flour lower values (6.86%) were obtained as compared with tarwi flour from
Egypt (21.73%) presenting 10% less protein content than that of the present work [16].
One of the most important characteristics expected in flours is a high starch content,
but the Andean crop flours presented a large variability, with taro showing the highest
values (p < 0.05), while most of the Andean crops mainly showed intermediate values
(Table 1). The starch content of achira flour was slightly lower with respect to taro flour,
with only 7.8% less starch, followed by arracacha and camote flour with 17–19% less starch
content, while oca and mashua flours had a considerably lower starch content, which was
around 31–37% less. Tarwi flour showed a marked lower starch content which was high
compared with the value (1.3%) reported by Villacrés, et al. [26] in debittered lupino. The
starch content of taro in the present work was similar to that of taro from the Kanchannaburi
(region of Thailand) and lower (59.8–72.62%) than that of some other varieties from several
regions (Chiang Mai, Phetchaburi and Saraburi) in Thailand, attributing the drop in starch
content to the decrease in average rainfall in the area [9]. The starch values in the present
work are rather higher to those reported by Moorthy, et al. [43] in fresh tubers of arracacha
(20%) of taro (10–18%), camote (12–30%) and oca (12%) from Andean regions of Peru;
these authors mentioned that the values could be associated with genotypic characteristics,
climatic and environmental factors and the state of maturation. The starch content of achira
in the present work was similar to that of medium particle size achira flours (42–80 mesh),
from tubers of the Conchal region (altitude 591 masl and subtropical climate) in Brazil [7].
These authors observed that according to the particle size selected for these flours, the
starch content could vary up to 20%; thus, in flours of sizes > 32 mesh, 42–80 mesh and
125–400 mesh, the starch content was 50.6%, 60.2% and 68.4%, respectively, indicating
that large agglomerates could accumulate in the first two fractions. A similar effect was
observed in yam (Ipomoea batatas) flours from Hebei (China), and the starch percentages
obtained (43.58%), similar to those of the present work, presented a particle size of 355 µm;
however, with particle size 75 µm, these authors obtained a somewhat higher content
of starch (61.90%) [44]. The increase in starch with smaller particle sizes is attributed
to the breakage of the flour structure so more active sites are exposed for enzymatic
degradation [45]. In parallel, it has also been observed that the sugar content may increase
slightly for the finest particle sizes, while decreasing for medium and coarse particle sizes,
attributing this fact to the hydrolysis of starch into oligosaccharides and monosaccharides
in the flour [44].
In some Andean flours, the carbohydrates are closely associated with the presence of
starch content. Thus, in tarwi, taro and even achira, a great proportion of carbohydrates
Agronomy 2021, 11, 1693 8 of 28

were starch (~86%, 93%, 75%, respectively). However, this ratio decreased drastically in
camote and arracacha flours (~55%), while the starch content in total carbohydrates of oca
and achira was markedly lower (~39%), which is associated with the high sugar content
characteristic in these crops [46,47].
The amylose content ranged 1.95–15.2% (p < 0.05). The highest values were found
in achira flour and the lowest in tarwi flour (Table 1). Typically, amylose is found in
a proportion of between 15–20% in starch molecules [48]. Nevertheless, in the present
work the relation of amylose with respect to starch is much higher in some flours, such as
mashua (43.58%), oca (34.50%) tarwi (33.39%) and achira (29.11%), while lower percentages
were found in camote, taro and arracacha with the lowest amylose content in starch (15.5%,
14.9% and 10.49%, respectively). The amylose: amylopectin or amylose to starch ratio, in
addition to being explained by the botanical origin of the crop, determines the morphology
and crystalline organization of the starch [48]. The amylose content in starch in taro
flour is much lower than that found in varieties of white and purple mallanga (Colassia
esculenta) from Colombia, 20.5% and 18.32%, respectively [49], while the varieties harvested
in Cameroon have much more variable ranges (16.5–30.8%) [49,50]. Higher amylose to
starch ratio has been found in camote of different cultivars from Thiruvananthaputam,
India (20–25%) [51]. However, the amylose to starch ratio in 10 varieties of taro from areas
of Thiruvananthaputam (India), ranged from 14.0% to 19.4%.
In addition to resistant starch, the higher the amylose content, the lower the di-
gestibility of the starch, considering that amylose content favors a more compact structure,
therefore making it less susceptible to enzymatic hydrolysis [14,48]. In this sense, the latter
authors observed that different camote genotypes might have different compositions and,
therefore, present a different digestibility behavior.
The caloric contents of tuber flours are close among them, and quite similar to cereal
flours, such as wheat flour (~354 kcal/100 g), with the exception of mashua flour which
presented a markedly inferior caloric content (p < 0.05) (Table 1). From a nutritional point
of view, most tubers and legumes have a higher proportion of resistant starch/total starch
than cereals [52], so nutritionally they would be of great interest in the daily diet.

3.2. pH and Acidity

The pH in farinaceous products is of great importance due to the influence it may
have on the stability and sensory characteristics of the products in which the flours are
incorporated. The pH values showed that these types of flour could be considered as
slightly acidic (Table 1). All values are in a narrow range, between 5.85 and 6.41, being the
lowest in camote and mashua, and the highest in oca and tarwi (p > 0.05). In food, weak
acids are mostly found because they only dissociate partially and do not have a severe
effect on pH, compared with strong acids [53]. Regarding acidity, mashua flour had the
highest value; this value could be associated with the presence of oxalic and ascorbic acids
reported in the composition of this tuber [54]. The rest of the Andean crop flours presented
percentages that ranged from 0.12 to 0.50%. In this connection a measure of stability of
the flours is linked to the percentage of acidity that should not exceed 2% (CODEX STAN
151-1989 (Rev. 1-1995) [55].

3.3. Color and Visual Appearance

Figure 1 shows the different Ecuadorian Andean flours and their respective crops of
origin. The coloration as well as the granulometry of the different flours can be seen at
a first glance. The color of food is a characteristic that consumers associate with the quality
of the products and it is generally the first impression that the consumer perceives when
purchasing a food. In the case of flours, the color allows or limits their use as ingredients
in the preparation of different classic foods, but in these alternative flours, color can also
mean an opportunity to design new products.
 Figure 1 shows the different Ecuadorian Andean flours and their respective crops of
origin. The coloration as well as the granulometry of the different flours can be seen at a
first glance. The color of food is a characteristic that consumers associate with the quality
of the products and it is generally the first impression that the consumer perceives when
purchasing a food. In the case of flours, the color allows or limits their use as ingredients
Agronomy 2021, 11, 1693 9 of 28
in the preparation of different classic foods, but in these alternative flours, color can also
mean an opportunity to design new products.

Visual appearance of
Figure1.1.Visual
Figure ofthe
theEcuadorian
EcuadorianAndean
Andeancrops andand
crops their corresponding
their flourflour
corresponding produced.
pro-
duced.
The results of color measurement are shown in Table 2. Due to the different nature
of the
TheAndean
results crops,
of colorthe parameters showed
measurement are shown a significant
in Table 2.difference
Due to the(pdifferent
< 0.05) with
naturethe
exception of ◦ H (tone). L* values were in a range of 59.2–78.66, which indicates that the ACF
of the Andean crops, the parameters showed a significant difference (p < 0.05) with the
mostly presented
exception light L*
of °H (tone). colors. Mashua,
values were inoca, achiraof
a range and camote flours
59.2–78.66, whichwere slightly
indicates darker,
that the
and they did not exceed 70, probably attributable to the high content of sugars
ACF mostly presented light colors. Mashua, oca, achira and camote flours were slightly and proteins,
as welland
darker, as the effects
they of degradation
did not of phenolic
exceed 70, probably components,
attributable to theincluding chlorophyll
high content and
of sugars andits
derivatives, anthocyanins (cyanidins, pelargodins and peonidins), proanthocyanins,
proteins, as well as the effects of degradation of phenolic components, including chloro- and
carotenoids
phyll (α-β carotenes),
and its derivatives, which affect
anthocyanins the Maillard
(cyanidins, reactions
pelargodins andand caramelization
peonidins), [56].
proantho-
Moreover, the low luminosity of achira could be due to the presence of certain enzymes
such as polyphenol oxidase that contributes to enzymatic browning [57]. Regarding a*,
Andean crop flours showed redness values in a range between 0.32 and 10.83, where oca
and achira flour presented similar values (p < 0.05). The higher a* values were for camote
and mashua (p > 0.05) due to the presence of flavonoids, antocyanins, phenolic acids and
carotenoids [58–60]. The color of the Andean crops studied displayed an orange and yellow
coloration in fresh, also attributable to the content of flavonoids and carotenoids. Mashua
flour registered the highest values for parameter b*, followed by tarwi and oca, since the
flours resembled the color of the original crops. The chromaticity (C*) results of mashua
flour showed the highest values (40.81), approaching the area of the most saturated yellows.
This effect can be attributed mainly to Maillard reactions and caramelization that occur in
Agronomy 2021, 11, 1693 10 of 28

the dehydration process, due to the presence of reducing sugars (aldehyde or ketone group)
and amino acids (free amino group) in this crop, which favor the development of brown
color. The lowest value for chromaticity was for camote, and the rest of the samples had
intermediate values. Regarding the tone (◦ H), camote flour presented the lowest values
(44.40), with a slight shift towards the area of orange tones. This can be attributed to the
fact that at temperatures above 66 ◦ C and prolonged dehydration times, changes in the
permeability of the cell membrane occur and, therefore, natural pigments in food such as
carotenoids, niacin and riboflavin migrate [61,62]. On the other hand, arracacha, tarwi,
taro, oca, achira, and mashua flours shifted in the CIELAB space towards intense yellows,
probably due to water loss, and without alteration of pigments, the yellow coloration in
these flours is enhanced. Finally, the whiteness index (WI) of taro presented the highest
values, very close to those reported by Aboubakar, et al. [50] in a different variety of taro
flour from Cameroon.
Table 2. Color properties of andean crops flours.

Sample Camote Oca Mashua Achira Arracacha Taro Tarwi

e d g f c a
L* 64.18 ± 0.12 69.00 ± 0.28 59.20 ± 0.21 61.78 ± 0.62 72.08 ± 0.26 78.66 ± 0.37 77.37 ± 0.14 b
a* 8.17 ± 0.20 b 5.26 ± 0.14 c 10.83 ± 0.12 a 5.89 ± 0.35 c 4.46 ± 0.11 d 2.31 ± 0.52 e 0.32 ± 0.13 f
b* 7.89 ± 0.60 g 22.71 ± 0.24 c 39.34 ± 0.18 a 21.40 ± 0.15 d 18.98 ± 0.14 e 12.62 ± 0.07 f 25.06 ± 0.11 b
C* 11.37 ± 0.30 g 23.49 ± 0.16 c 40.81 ± 0.18 a 22.20 ± 0.15 d 19.45 ± 0.12 e 12.84 ± 0.11 f 25.36 ± 0.14 b
◦H 44.40 ± 0.50 g 83.95 ± 0.40 c 77.30 ± 0.30 e 92.59 ± 0.80 a
68.82 ± 0.60 f 78.94 ± 0.50 d 86.80 ± 0.60 b
WI 62.43 ± 0.35 c 61.12 ± 0.47 d 42.30 ± 0.23 f 55.80 ± 0.30 e 65.97 ± 0.43 b 75.10 ± 0.40 a 66.97 ± 0.35 b
Different letters (a, b, c, d . . . ) indicate significant differences between samples.

3.4. Granulometry
In the production of farinaceous derivatives, the fineness modulus is a parameter
that influences several quality attributes such as the dispersion of powdery material,
rheological properties of the flours and doughs, texture attributes, solubility in water, and
water and oil retention capacity [63,64]. The fineness index ranged from 2.87 to 3.84, which
indicates that the particle size and size distribution corresponds to flours with medium-
sized particles (Table 3). The whole flours obtained from Andean crops showed these
fineness moduli because the presence of certain structures (such as cellulose, hemicellulose,
lignin, and pectins, among others), corresponds to the fraction that provides the peel of
tubers, rhizomes and seed, which contribute to the generation of coarser particles [65].
There were significant differences among ACF, with the highest fineness index in tarwi
(p < 0.05), perhaps because the peel ratio is higher in this legume in relation to its size.
Camote, mashua and taro showed a lower and similar fineness index, while the lowest
corresponded to achira and oca (p < 0.05). A low fineness index is recommended for
bulk flowing since it limits the surface contact and cohesion between flour particles [13].
These authors obtained values of 2.9 for polydispersity index in taro flours, showing
a bimodal distribution. The uniformity index shows that flours have a higher amount of
thick, rather than fine or medium-sized particles (p < 0.05) with the exception of achira flour,
as consequence of the particular content of fine starch of this crop. However, it is important
to note that the results of the grinding process were similar in all samples, and even though
there are fractions of different sizes in the flours with differences in the fineness indexes, all
of them are categorized as medium-sized.

3.5. Bulk Density

Bulk density is a complex property in farinaceous products and it is of great impor-
tance for economical and functional reasons. While high bulk density is desirable for
reducing shipping and packaging costs, low bulk density could influence the powder prop-
erties such as flowability and instant characteristics [66]. In the current study, values ranged
from 0.47 to 0.71 (p < 0.05) (Table 3). The highest apparent density values were obtained
in the oca samples (p < 0.05); this result is concordant with Subramanian, et al. [67] who
reported that at higher moisture levels, bulk density increases. In addition, the medium
Agronomy 2021, 11, 1693 11 of 28

size of the particles also favors the density of flour, because high densities are associated
with fine particles, since they tend to agglomerate occupying a greater volume due to low
resistance to compaction [68]. When particles are limited by a specific volume, they tend to
organize randomly and empty spaces form between the particles, so this irregularity will
increase the apparent density [69].

Table 3. Granulometry properties and Bulk density of Andean crops flours.

Uniformity Index
Sample Fineness Index (g/10 g Sample) Bulk Density (g/cm3 )
Thick Medium Fine
Camote 3.29 ± 0.05 b 6.05 ± 0.01 b 1.39 ± 0.03 f 2.55 ± 0.01 c 0.62 ± 0.01 bc
Oca 2.88 ± 0.01 d 5.31 ± 0.05 e 1.32 ± 0.04 f 3.37 ± 0.04 b 0.71 ± 0.01 a
Mashua 3.26 ± 0.08 bc 5.89 ± 0.06 c 1.50 ± 0.05 e 2.49 ± 0.11 c 0.65 ± 0.01 bc
Achira 2.87 ± 0.07 d 3.22 ± 0.02 f 1.75 ± 0.01 d 5.03 ± 0.03 a 0.63 ± 0.01 bc
Arracacha 3.12 ± 0.02 c 5.64 ± 0.06 d 1.85 ± 0.01 c 2.51 ± 0.05 c 0.67 ± 0.04 ab
Taro 3.33 ± 0.01 b 6.01 ± 0.01 bc 1.96 ± 0.01 b 2.04 ± 0.01 d 0.60 ± 0.01 c
Tarwi 3.84 ± 0.08 a 6.39 ± 0.03 a 2.99 ± 0.03 a 0.53 ± 0.07 e 0.47 ± 0.01 d
Different letters (a, b, c, d . . . ) indicate significant differences between samples.

3.6. Scanning Electron Microscopy (SEM)

Camote flour showed globular, slightly ovoid, and irregular granules with a smooth
and loose surface (Figure 2A). As Souza, et al. [14] described, non-starch compounds,
probably proteins, were also observed. The particle size distribution was small (Table 4),
mainly between 0–10 µm and 10–20 µm, with a reduced proportion of larger granules.
Souza, et al. [14], observed different distribution profiles in four varieties of camote flour
from Brazil; those of genotype G2 and G4 are similar in size distribution to that of the
present work, while those of genotype G1 and G3 have a larger size distribution.

Table 4. The particle size distribution of andean crops flours.

Particle Size * (%) Camote Oca Mashua Achira Arracacha Taro Tarwi
0–10 µm 43.3 ± 0.02 - 40 ± 0.05 - 21.7 ± 0.02 90.6 ± 0.02 50.0 ± 0.01
10–20 µm 53.3 ± 0.01 25.0 ± 0.02 40 ± 0.04 - 60.9 ± 0.01 6.3 ± 0.01 -
20–30 µm 3.3 ± 0.04 9.4 ± 0.06 3.2 ± 0.01 17.4 ± 0.03 3.1 ± 0.02 -
30–40 µm - 34.4 ± 0.03 20 ± 0.02 38.7 ± 0.05 - - 50.0 ± 0.01
40–50 µm - 18.8 ± 0.04 19.4 ± 0.03 - - -
50–60 µm - 12.5 ± 0.02 38.7 ± 0.02 - - -
Average particle
12.14 34.54 14.8 44.89 8.97 5.62 20
size (µm)
Piled-up Size * (%)
0–30 µm - - - - - 100 -
30–60 µm - - - - - - 100
60–90 µm - - 100 - - - -
Average piled-up
- - 80.36 - - 19.51 42.22
particles size
* Particle size is grouped in intervals of sizes of average diameter measured in µm.

Oca flour showed an oval-shaped granule appearance, slightly elongated, with

a smooth surface, and occasionally some deflated granules were observed (Figure 2B).
The particle size distribution (Table 4) showed sizes much larger than those of the camote
flour granules, with sizes widely distributed from 10–20 µm to 50–60 µm, although parti-
cles of 10–20 µm and 30–40 µm were predominant. A similar shape and size have been
observed in the Mexican oca flour granules (Hernández-Uribe, et al. [70].
In mashua flour (Figure 2C), in addition to starch granules, non-starch components
were observed around the granules in most cases; these structures could be mainly
fiber and/or protein present in this type of Andean crops, similar to those reported by
Agronomy 2021, 11, 1693 12 of 28

Pacheco, et al. [24]. The starch granules in the flour had an irregular spherical-like shape.
The particle size distribution indicates the presence of two populations distributed uni-
formly in the two smaller sized fractions (40% in each one of them) and in the intermediate
(30–40 µm) fraction (20%), that correspond mainly to isolated starch granules (Table 4).
Additionally, some structures composed of granules and non-starch component are mixed
forming a large piled-up organization (60–90 µm).

A B

D
C

E F

A) Camote
B) Oca
C) Mashua
D) Achira
E) Arracacha
G F) Taro
G) Tarwi

Figure 2. Micrographs of andean crops flours with 546× magnification.

Figure 2. Micrographs of andean crops flours with 546 X magnification

Agronomy 2021, 11, 1693 13 of 28

In addition to the granules, achira flour presented certain dense particles which could
be proteins and fibers (Figure 2D), also described by Andrade-Mahecha, et al. [7]. The
starch granules of this rhizome have a characteristic oval and flattened shape. The particle
size distribution (Table 4) indicates a wide polydispersity in large granules, even greater
than in oca flour, being the most abundant between 30–40 µm and 50–60 µm.
The starch granules in arracacha flour showed an irregular globular and/or irregular
appearance, sometimes rounded and independent (Figure 2E). The distribution of their
granules (Table 4) reveals that this flour has the smallest sizes most granules being within
the range 10–20 µm. Both the appearance and the size are similar to those observed
in arracacha starch from Colombia, with mean values of 4–12 µm [35], 9.81–13.74 µm
(Pinzon et al., 2020), and 20–22 µm from Peru [71,72].
Starch granules in taro flour were small and asymmetrical (Figure 2F and Table 4).
The size distribution was very irregular, being mostly between 0–10 µm, with some scarce
oversized granules, which appeared in an aggregated or piled-up structure, with an average
size of around 19.51 µm (Figure 2F and Table 4). These dimensions and appearance are
similar to those reported by other authors in taro flours from Cuba (2.7 µm on average) [13]
and Peru (0.3–10.0 µm) [51]. Wongsagonsup, et al. [9] found much larger granule sizes in
taro flours from Thailand, ranging from 52.17 to 67.63 µm, and indicated that this might be
consequence of aggregated starch, because by isolating the starch, granule sizes ranged
from 2.14–3.59 µm. At the bottom of the micrograph, other non-granular structures were
clearly observed, which are attributed to other flour compounds.
The micrograph of tarwi flour showed the presence of two types of particles and
aggregates. Both particles were surrounded by other structures, that according to the
composition, could be mainly proteins (Figure 2G), corresponding to the profile obtained
in the particle size distribution (Table 4).
The aggregate could be composed of starch, proteins and fibers, which could favor
the piled-up structure in some cases, as mashua, forming structures with a quite large
average particle size, or in the case of tarwi, with medium-size aggregates with an average
of 42.22 µm (Table 4).
Regarding aggregate sizes, the smallest corresponded to taro flour, followed by tarwi
and mashua, while in the rest of the flours these aggregates were not appreciated; however,
other compounds were observed in the micrograph. With respect to the average size of
starch granules, achira and oca flours presented notably larger granules than tarwi, camote,
mashua and arracacha flours, which had intermediate values, while the smallest granules
corresponded to taro (Table 4). Starch granule size has been observed to influence the
amount of resistant starch, since an increase in amylose favors granule compaction and
density, which contributes to a slower digestion [14,48].

3.7. Differential Scanning Calorimetry (DSC)

The results of the DSC analysis are shown in Table 5. The lower gelatinization temper-
ature range (∆ Tc–To) was observed in mashua flour (8.43 ◦ C) as compared with the other
flours (around ~8–12 ◦ C). On the contrary, in tarwi flour the required temperature reached
up to 32.68 ◦ C. The lowest gelatinization peak (Tm) corresponded to arracacha and achira
(p < 0.05) and the highest to camote flour. Differences in the thermal properties can vary
according to the botanical species of the crop. Therefore, low gelatinization temperatures
could be associated with a high amylose content in starch [73]. However, this relation
was not shown in the present work since, for example, camote flour presented a high
Tm and a low amylose content in starch. The Tm of camote ranged from 70.2 to 77 ◦ C in
44 varieties from the Philippines, while it was 74 ◦ C in 2 varieties from Peru [51]. In achira
flour of different granulometries (>32 mesh and 42–80 mesh from Brazil) no significant
differences in the Tm (72.0 and 71.8 ◦ C), To (66.9 and 66.8) and Tc (77.4 and 77.9) were
observed, and no differences were observed either in the thermal properties of achira from
Colombia for the aforementioned parameters (71.6, 67.3 and 77.0, respectively) [7]. These
authors observed that the high fiber content, as well as the protein and lipids present in the
Agronomy 2021, 11, 1693 14 of 28

flour, favor the increase of Tm due to a protective action of these components, through the
inhibition of hydration of the starch granules and therefore, of gelatinization, favoring low
gelatinization enthalpy values.

Table 5. Differential scanning calorimetry (DSC) results for andean crops flours.

To Tm Tc ∆H
Samples
(◦ C) (◦ C) (◦ C) (mJ/mg)
75.76 ± 0.7 a 81.48 ± 0.1 a ab 0.55 ± 0.1 c
Camote 87.21 ± 0.4
Oca 68.58 ± 0.6 bc 72.89 ± 0.6 bc 78.03 ± 0.6 b 0.87 ± 0.1 ab
Mashua 69.86 ± 0.1 b 73.81 ± 0.7 b 78.29 ± 0.9 b 1.42 ± 0.5 a
Achira 64.03 ± 0.1 cd 68.74 ± 0.4 c 73.02 ± 0.1 b 0.54 ± 0.1 c
Arracacha 62.26 ± 0.3 d 68.46 ± 0.1 c 74.26 ± 0.4 b 0.76 ± 0.1 b
Taro - - - -
Tarwi 64.54 ± 0.9 cd 79.89 ± 0.6 ab 97.22 ± 0.6 a 1.41 ± 0.5 a
To: ‘onset’ initial temperature, Tm: ‘meltinG0 peak temperature, Tc: ‘conclusion’ or final temperature, ∆H:
gelatinization enthalpy. Different letters (a, b, c, d) indicate significant differences between samples.

The highest gelatinization enthalpy value was found in mashua and tarwi flours
(p < 0.05). Similar results were reported by Pacheco, et al. [74], who indicated that mashua
starch has a greater number of double helical areas in the amylose chains, and therefore
requires more energy to break the number hydrogen bonds between the glucan chains [75].
The starch is not the main component of Andean crop flours, but the presence of other
components such as cell wall materials, proteins, pectins, among others, can influence the
measurement [76]. The ∆H indicates the energy required to break the molecular interactions
within the starch granules during the gelatinization process. Low ∆H values found in
all samples could be due to some degree of modification or denaturation of starch and
protein that occurs during drying [23], so that a previous partial fusion of the amylopectin
crystals may have occurred [7]. On the other hand, it should be noted that in flours from
camote and tarwi, no phase transition is observed, while no evidence of thermal events was
detected in taro. It is possible that starch may be fully gelatinized during the drying process,
which was developed at 60 ◦ C in the studied Andean crops. According to Torres, et al. [49],
the gelation temperature of taro starch from Colombia is 55 ◦ C. However, in tarwi flour, the
absence of phase transition for starch can be attributed to the low starch content (0.6%) [77].
The Tm values of the rest of the flours could be associated with the presence of compounds
such as proteins, lipids and fiber that degrade at higher temperatures but with a lower
energy consumption [76]. Therefore, non-starch constituents of the flours play a marked
role in starch gelatinization, where, in addition to the protecting effect on the surface of the
granules, some water competition could also contribute to retard starch gelatinization [13].

3.8. Swelling Power and Solubility

The swelling factor is used to evaluate the integrity of the starch granules and is
directly related to the increase of temperature. This property is associated to the amy-
lopectin content, while amylose is considered a diluter and inhibitor of swelling [78].
Therefore, swelling capacity increases linearly with the heat of gelatinization and decreases
linearly with amylose content [79]. Moreover, the interaction between the starch chains
inside the amorphous and crystalline domains of the granules is affected by the ratio amy-
lopectin/amylose, the bond distribution and molecular weight characteristics of amylose
and amylopectin [80]. In flours, swelling could be related to starch and other compounds
that also compete for water, as polar residues of amino acids forming part of proteins and
the highly hydrophilicity of fibers [7]. In this study, low values for swelling were noted in
the range of temperatures evaluated, increasing slightly at 70 ◦ C in taro and mashua flours
(Figure 3A). The exception was observed in achira, in which low values at temperatures
below 60 ◦ C were observed, while above this temperature swelling increased, the values
doubling at 80 ◦ C. This behavior in achira flour could be attributable to the breaking of
hydrogen bonds; water molecules bind to the hydroxyl groups released, and the gran-
Agronomy 2021, 11, 1693 15 of 28

ules expand, exuding amylose [7]. Moorthy [51] attributed the low swelling in camote
starch to the high degree of starch granule intermolecular associations. In tarwi, lipids
and proteins could affect swelling because the gelatinization is delayed by the coating
of starch, preventing it from absorbing water and resulting in reduced swelling capac-
ity [81]. In this sense, Andrade-Mahecha, et al. [7] compared the swelling obtained by
flour and starch of achira from Brazil, observing that swelling is greater in flour than in
starch at temperatures < 65 ◦ C, while at temperatures > 60 ◦ C the behavior is reversed,
and swelling is greater in starch. Therefore, at low temperatures, the swelling of flour is
due to the presence of proteins and fibers with polar charge; while the swelling
Agronomy 2021, 11, x FOR PEER REVIEW 16 of power
29 at
high temperatures is attributed to starch granules, both for their large size and for their
amylose content.

Figure 3. (A) Swelling power; (B) solubility of flours as a function of the temperature (50–80 ◦ C).
Figure 3. (A) Swelling power; (B) solubility of flours as a function of the temperature (50–80 °C).

The solubility, which was related to the presence of diverse soluble molecules, showed
3.9. Water Absorption Capacity (WAC)
reduced values in all flours at low temperatures and increased noticeably with the rise
The water absorption capacity of the different flours is shown in Figure 4. Oca and
of temperature (Figure 3B). The lowest values found at all temperatures were for tarwi
achira flours showed the highest values at 80 °C; in oca flour its◦ values doubled at 60 °C
flour (p < 0.05), observing a light increase (p < 0.05) from 60 C, but not reaching more than
and then continued to◦ rise until reaching 80 °C while the increment was gradual in achira
5% solubility at 80 C, as expected due to the low starch content of this legume. The rest of
flour (p < 0.05). Torres, et al. [49] proposed that the ability of flour to absorb water is asso-
tuber or rhizome flours showed a very similar evolution; at low temperatures (≤60 ◦ C) flours
ciated with the damage suffered by starch granules at temperatures above 60 °C, which
presented low solubility (3–5%), but with the increase of temperature, from 60 ◦ C onwards,
causes the release and union of hydrophilic groups with water. All flours tended to in-
the solubility
crease their WAC increased drastically,
as temperature wasreaching similar
increased; valuescamote
however, in achira, taro
flour and oca
barely floursa(~22%)
showed
(p < 0.05), showing the highest values in camote flour (~26%) (p < 0.05) at 80 ◦ C.
significant increase of 1.33% between 50 and 60 °C and mashua flour of 3.63% (p < 0.05)
mainlyAt low50temperatures,
from to 60 °C, whilemolecules
the increasesuch as proteins,
in taro flour wassugars, and soluble
higher (5.2%), fiber can con-
more sharply
tribute to the solubility of the flours, whose composition could be very
from 70 °C onwards. No relationship was found between the starch content, or the amountvariable depending
of protein and fiber, or the gelatinization temperature in each flour and the WAC. How-
ever, flours with a higher WAC were those in which starch grains presented a larger par-
ticle size, determined by SEM and a wider polydispersity of sizes, such as oca and achira
flours (Figures 2 and 4, Table 4). Some authors note that with smaller granule sizes, where
the surface area of exposure and contact to water increases, and the ability to retain water
Agronomy 2021, 11, 1693 16 of 28

on the nature of the crops, mainly on whether they come from legumes or tubers [7,63].
Therefore, the temperature at which starch gelatinizes in each flour is an important factor in
swelling. The increase in solubility in arracacha starch occurs with increasing temperature
between 50 and 60 ◦ C, due to starch gelatinization (55 ◦ C) and leaching of solubilized amy-
lose [7]; small-sized molecules will leach more easily, increasing solubility. Furthermore,
the increase in small-sized molecules may be favored by a weak starch granule structure
that favors starch depolymerization [71]. Another factor to take into account regarding
solubility is the presence of a large number of weak interactions in the starch granules
which immobilize them, irrespective of the swelling. Thus, starch extracted from camote
from the Peruvian variety only showed an increase in solubility of around 10% with high
temperatures [51].

3.9. Water Absorption Capacity (WAC)

The water absorption capacity of the different flours is shown in Figure 4. Oca and
achira flours showed the highest values at 80 ◦ C; in oca flour its values doubled at 60 ◦ C
and then continued to rise until reaching 80 ◦ C while the increment was gradual in achira
flour (p < 0.05). Torres, et al. [49] proposed that the ability of flour to
Agronomy 2021, 11, x FOR PEER REVIEW absorb
17 of 29 water is
associated with the damage suffered by starch granules at temperatures above 60 ◦ C,
which causes the release and union of hydrophilic groups with water. All flours tended to
increase
Tarwi their WAC asa slight
flour showed temperature
increase inwas increased;
its WAC at 60 °Chowever,
(p < 0.05),camote flour barely showed
mainly attributed
toa proteins
significant increase
(native of conformational
or with 1.33% betweenchanges, 60 ◦ C andeither
50 and produced mashua flour
during flourofpro-
3.63% (p < 0.05)
cessing
mainly orfrom
during50this 60 ◦ C, while
to thermal treatment) but this property
the increase in tarodid notwas
flour increase with(5.2%),
higher an incre-more sharply
ment ◦ C onwards.
fromin70temperature (p < No
0.05). This fact canwas
relationship be due
foundto the reducedthe
between amount
starchofcontent,
starch and or the amount
the high content of proteins in this flour, which could suffer a denaturation at high tem-
of protein and fiber, or the gelatinization temperature in each flour and the WAC. However,
peratures and thus reduce the WAC. The high protein content present in tarwi could pre-
flours with a higher WAC were those in which starch grains presented a larger particle
vent the diffusion of water into starch granules because polar side chains establish strong
size, determined
hydrogen by SEMaand
bonds by forming a wider
network polydispersity
which limits the swellingof sizes, such[82],
of starch as ocaandand
pro-achira flours
(Figures
teins do not2 have
and good
4, Table 4). Some
swelling authors
properties under note
the that
testedwith smaller
conditions. granule
For tarwi, insizes,
the where the
surfacework
present areathere
of exposure and contact
was no relationship to water
between WACincreases,
and the size and the ability
distribution of to
theretain water
increases
structure as wellby[13].
observed SEM,The waterbecause
perhaps absorption
the tworate of arracacha
populations foundstarch
(small granules
and me- from Peru
dium
was sizes),
7% < 55 and◦ C
because starch is very
and increased scarce,
to 9% at 60 ◦ Cit [71],
and is surrounded by protein,
being slightly higher as previ-
than those of the
ously mentioned.
arracacha flour of the present work.

Figure 4. Water absorption capacity (WAC) of flours as a function of the temperature (50–80 ◦ C).
Figure 4. Water absorption capacity (WAC) of flours as a function of the temperature (50–80 °C).

Tarwi flour
3.10. Rheological showed a slight increase in its WAC at 60 ◦ C (p < 0.05), mainly attributed to
Characterization
proteins (native or with conformational changes, produced either during flour processing
The profiles obtained for the storage dynamic modulus (elastic) (G’), loss dynamic
modulus (viscous) (G”) and phase angle (tan δ) as a function of the angular frequency
(rad/s) are shown in Figure 5. The doughs developed with the Andean crop flours are
classified as viscoelastic fluids because the lag between stress and strain are in the range
from 0 to 90° with a predominance of elastic properties over viscous ones (Chang, et al.
[83]. For most samples, G’ and G” increased with the rise in frequency, displaying a dom-
Agronomy 2021, 11, 1693 17 of 28

or during this thermal treatment) but this property did not increase with an increment in
temperature (p < 0.05). This fact can be due to the reduced amount of starch and the high
content of proteins in this flour, which could suffer a denaturation at high temperatures and
thus reduce the WAC. The high protein content present in tarwi could prevent the diffusion
of water into starch granules because polar side chains establish strong hydrogen bonds by
forming a network which limits the swelling of starch [82], and proteins do not have good
swelling properties under the tested conditions. For tarwi, in the present work there was
no relationship between WAC and the size distribution of the structure observed by SEM,
perhaps because the two populations found (small and medium sizes), and because starch
is very scarce, and it is surrounded by protein, as previously mentioned.

3.10. Rheological Characterization

The profiles obtained for the storage dynamic modulus (elastic) (G0 ), loss dynamic
modulus (viscous) (G00 ) and phase angle (tan δ) as a function of the angular frequency
(rad/s) are shown in Figure 5. The doughs developed with the Andean crop flours are
classified as viscoelastic fluids because the lag between stress and strain are in the range
from 0 to 90◦ with a predominance of elastic properties over viscous ones (Chang, et al. [83].
For most samples, G0 and G00 increased with the rise in frequency, displaying a dominant
solid-like behavior, which indicates that the system develops a certain structural level, as
a strong gel [84]. Taro flour was the exception, where G00 slightly increased more than G0 ,
indicating an unstructured and viscous behavior. This behavior is not in line with that
observed by Arıcı, et al. [85], where taro flour addition in increasing amounts (up to 25%)
to wheat flour, increased both G0 and G00 , being always G0 > G00 for all angular frequencies
tested. This is associated with the small size of the taro granules, which interact better
with the other components of the flour such as proteins, lipids and fibers due to a larger
exposure surface [86]. These authors give great importance to the presence of mucilage;
that is, mucilage contributes to the predominance of the solid gel-like structure in taro
flour, so it could occur that in the present work, in this taro variety from Ecuador, mucilage
content is lower compared with the taro flour from the Anamur region of Mersin (Turkey)
mentioned by these authors. Initially, at low frequencies, taro flour showed quite low G0
and G00 values, duplicating at angular frequencies of 30 rad/s (Table 6), which can lead
to a break from starch granules [87] and an entanglement of the components. In oca flour,
a crossover between G0 and G00 at high frequencies took place, displaying a rather viscous
character. This means that the oca flour solution showed a rigid solid-like behavior at lower
frequencies (G0 > G00 ) and a liquid-like behavior at higher frequencies (G0 > G00 ), which
could be related to the entanglement of networks with reduced strength starch [88].
Table 6. Mechanical spectra fit-parameters of dynamic rheological properties of flours at different angular frequencies
(rad/s), G0 , G00 , (Pa), and flow behavior index (n).

Rheological
Camote Oca Mashua Achira Arracacha Taro Tarwi
Parameters
n 0.1513 ± 0.02 ab 0.1651 ± 0.01 ab 0.1558 ± 0.01 ab 0.1394 ± 0.02 ab 0.1813 ± 0.01 a 0.1201 ± 0.02 b 0.1201 ± 0.02 b

ω G0 3259.00 ± 0.49 cz
347.02 ± 0.06 gz
635.21 ± 0.10 fz 3837.40 ± 0.53 az
1130.00 ± 0.20 ez
2259.30 ± 0.39 dz
3528.00 ± 0.42 bz
(1 rad/s) G00 2465.90 ± 0.45 cz 296.43 ± 0.06 gz 578.45 ± 0.10 fz 2347.00 ± 0.42 dz 818.99 ± 0.17 ez 2609.00 ± 0.42 bz 2692.60 ± 0.41 az
Tanδ 0.76 ± 0.00 dz 0.85 ± 0.00 cz 0.91 ± 0.00 bz 0.61 ± 0.00 fz 0.72 ± 0.00 ey 1.15 ± 0.00 aw 0.76 ± 0.00 dz

ω G0 5452.21 ± 0.03 by 608.45 ± 0.00 gy 1.079.08 ± 0.01 fy 6165.21 ± 0.03 ay 2093.54 ± 0.01 ey 4063.73 ± 0.02 dy 5308.00 ± 0.02 cy
(30 rad/s) G00 4556.13 ± 0.03 ay 602.83 ± 0.00 gy 1.019.08 ± 0.01 fy 4295.34 ± 0.03 dy 1638.56 ± 0.01 ey 4509.65 ± 0.02 by 4496.99 ± 0.02 cy
Tanδ 0.84 ± 0.00 ey 0.99 ± 0.00 by 0.94 ± 0.00 cy 0.70 ± 0.00 gy 0.78 ± 0.00 fx 1.11 ± 0.00 ax 0.85 ± 0.00 dy

ω G0 6055.06 ± 0.02 bx 682.22 ± 0.00 gx 1.202.14 ± 0.00 fx 6790.65 ± 0.02 ax 2373.87 ± 0.01 ex 4580.18 ± 0.01 dx 5768.79 ± 0.01 cx
(60 rad/s) G00 5163.35 ± 0.02 ax 696.66 ± 0.00 gx 1.143.74 ± 0.00 fx 4858.37 ± 0.01 dx 1887.31 ± 0.01 ex 5041.72 ± 0.01 bx 4992.49 ± 0.01 cx
Tanδ 0.85 ± 0.00 ex 1.02 ± 0.00 bx 0.95 ± 0.00 cx 0.72 ± 0.00 gx 0.80 ± 0.00 fw 1.10 ± 0.00 ay 0.87 ± 0.00 dx

ω G0 6438.15 ± 0.01 bw 729.46 ± 0.00 gw 1.280.53 ± 0.00 fw 7185.52 ± 0.01 aw 2554.95 ± 0.01 ew 4912.20 ± 0.01 dw 6056.66 ± 0.01 cw
(90 rad/s) G00 5555.41 ± 0.01 aw 758.18 ± 0.00 gw 1.223.62 ± 0.00 fw 5221.34 ± 0.01 dw 2049.98 ± 0.00 ew 5381.60 ± 0.01 bw 5307.28 ± 0.01 cw
Tanδ 0.86 ± 0.00 ew 1.04 ± 0.00 bw 0.96 ± 0.00 cw 0.73 ± 0.00 gw 0.80 ± 0.00 fw 1.10 ± 0.00 ay 0.88 ± 0.00 dw

Different letters (a, b, c, . . . ) in the same line indicate significant differences between samples (p ≤ 0.05). Different letters (w, x, y, . . . ) in the
same column indicate significant differences in same sample for each parameter (p ≤ 0.05).
 taro (1.15–1.10) probably as a result of a strong interaction between the fiber and starch
present in the flour (14.90% and 59.98% respectively). Chaisawang, et al. [98] incorporated
xanthan gum to starch paste and observed a decrease in tan δ, attributing this behavior to
the opposite charges of starch and gum which contribute to form a compact structure.
Agronomy 2021, 11, 1693 Tarwi showed an increase of tan δ from 0.76 to 0.88, which indicates more solid-like 18 ofvis-
28
coelastic properties. Similar behavior was observed on partially substituted lupin on
wheat bread [99].

Figure 5. Mechanical spectra of dynamic rheological properties of flours vs. frequency (rad/s).
Figure
(A) 5. Mechanical
Storage modulus (Gspectra of dynamic
0 , Pa); (B) rheological
loss modulus properties
(G00 , Pa); of flours
(C) loss factor vs.δ.frequency (rad/s). (A)
tang
Storage modulus (G’, Pa); (B) loss modulus (G”, Pa); (C) loss factor tang δ.
Mashua and oca flours showed lower G0 and G00 , resulting in a weak gel compared
with achira, camote, tarwi and white arracacha. This behavior could be attributed to the
restricted granular swelling, lower water solubility [89,90] and lower amylose content in
both flours, and also to a higher content of lipids in oca flour (~1.06%). The presence of
lipids altered the viscoelastic properties of doughs, since G0 values were lower in flours in
which lipids were present [91,92]. Besides, the small size of starch granules observed in
mashua (~9.6 µ average size) contributes to low G0 and G00 values as was perceived in small
granules of potato starch fractions [93]. Achira and camote were the tubers with the highest
G0 values, which could be explained by their greater amylose and fiber contents (8.08%,
11.51% and 6.20%, 11.19%, respectively), which strongly interact in the polymeric matrix.
Similar results were observed when Arabic gum was added to improve the functionality of
Agronomy 2021, 11, 1693 19 of 28

tapioca starch [94]. Tarwi also had high G0 values and showed a typical solid-like behavior
with strong viscoelastic properties (G0 > G00 ). G0 ranged from 3528 Pa to 6056 Pa, and G00
from 2692 Pa to 5307 Pa. This behavior could be explained by the higher protein content
(52.82%), in which originates intermolecular interactions. Similar results were obtained by
Xu, et al. [95] in lupin and defatted lupin suspensions with 50% protein where G0 values
were much greater than those for G00 .
The tan δ behavior (Figure 5C) showed an increase of tan δ to values close to the unit
in oca (0.85–1.04) and mashua (0.91–0.96), which indicates the breakdown of the starch
structure and a greater viscous component, probably due to the presence of damaged
starch, as was observed in wheat flour [87]. Achira, white arracacha, camote and tarwi
presented tan δ values that ranged from 0.61 to 0.88 which increased with frequency
(Table 6), indicating a more elastic and a slightly stronger gel network that could be affected
by the chemical composition, especially by fiber and amylose contents. Similar results were
observed for orange-fleshed camote, where tan δ < 1 indicates a predominant elasticity over
viscous properties, sago starch [96] and camote starch, where the tan δ values were lower
after the addition of gums [97]. On the contrary, tan δ slightly decreased in taro (1.15–1.10)
probably as a result of a strong interaction between the fiber and starch present in the flour
(14.90% and 59.98% respectively). Chaisawang, et al. [98] incorporated xanthan gum to
starch paste and observed a decrease in tan δ, attributing this behavior to the opposite
charges of starch and gum which contribute to form a compact structure. Tarwi showed
an increase of tan δ from 0.76 to 0.88, which indicates more solid-like viscoelastic properties.
Similar behavior was observed on partially substituted lupin on wheat bread [99].
The values of flow behavior index (n) for all samples are shown in Table 6. In addition,
n values were less than 1, and exhibited the shear-thinning behavior characteristic of starch
materials. Other researchers obtained n values of 0.55 for purple camote flour [100]. The
flow behavior indexes (n) of arracacha were slightly higher than those of oca, mashua
and camote, tarwi and taro. Zhu, et al. [89], compared the flow properties of oca starch;
according to their results, the n value was ~0.25, a higher value than that obtained in the
present work with flour (0.16). Achira starch showed an n value of ~0.35 [101], white
arracacha starch showed an n of 0.61 and n’ 0.22 [90,102], taro starch n = 0.7 [103] and lupin
flour with wheat starch and egg used as pasta dough n = 0.34. [104]. The results of the flow
behavior of flours can be explained by structural differences in the composition, amylose
content, and amylopectin amounts and granule size.

3.11. Antioxidant and Total Phenol Content

The results obtained from the phenolic compounds and antioxidant activity in flours
from Ecuadorian Andean crops are shown in Figure 6. These results are not easily com-
parable with the literature, since there are hardly any references on these flours because,
the data are expressed in different ways, and the treatments of the raw materials are differ-
ent. Regarding phenol contents (Figure 6A), the values present a large variation, between
6.5–60.8 µg gallic acid equivalent (AGE)/g of a sample. Mashua flour had the highest value
(60.8 µg AGE/g of sample) (p < 0.05), which differs from that reported by Catunta [105] in
fresh samples of mashua (128–146 mg GA/100 g). These authors also reported 163 µmol
trolox equivalent/g in osmotically dehydrated mashua and 175 µmol trolox equivalent/g
in black mashua from Yunguyo (Puno, Peru), cultivated at an altitude of 3847 m. The
lower phenol content in mashua flour in the present work could be due to the difference in
composition because of the geographical location (despite Puno and Ambato being Andean
regions, there is an altitude difference of 3547 m between them); and, in addition, to other
characteristics such as the crop, or to a loss caused by the thermal drying treatment. The
total phenol content could be attributed to the presence of flavonoids, phenolic acids and
tannins; in turn, these components could be influenced by the optimal state of tuber matu-
rity and the effects of heat in the drying process [106]. The Folin-Ciocalteu assay is a widely
used method to determine the total phenol content, but there are other substances, such as
sugars and proteins, which react with the Folin-Ciocalteu reagent [107]. It is important to
Agronomy 2021, 11, 1693 20 of 28

consider this, since proteins and sugars are part of the composition of these flours. Values
around 20 mg GA/100 g are found in most of the flours, and the lowest phenol content
Agronomy 2021, 11, x FOR PEER REVIEW 21 of 29
corresponded to arracacha and tarwi flours (p < 0.05). The phenol content in oca flour
is similar to that found in oca tuber [108]. However, tarwi flour values are much lower
than those observed by the aforementioned authors. A total phenol content higher than
tubers, rhizomes
that found in theand grains
present [58,59,108].
work ABTS (110
was reported assaysµg showed
GAE/mg anextract)
antioxidant activity
in water of
extract
114 µ g/mL in the water extract of ◦
achira (Canna indica) rhizomes from Mysore
of achira (Canna indica) dried (45 C) rhizomes from the banks of Cauvery River (Mysore, (India), [32].
On the other
India), hand,
[32], and initcamote
was observed that debittering
flour (values ranged from three
28 varieties
to 1228 mg of tarwi
GAE/100(fromg)Peru)
from
produces a decrease
19 Philippine in ABTS
varieties, grown ofin
52.9%, and area
the same the subsequent
and under spray
similardrying produces
conditions as toaavoid
fur-
ther 8% decrease
possible in ABTS
differences due toactivity [109]. Villacrés,
these factors et al. [26]
[15]. In lupinus observed
grains a decrease
from Ecuador in the
(varieties
antioxidant
INIAP-450,activity of 96.13%
INIAP-451 in threeVillacrés,
and Criollo), varieties et
of al.
Ecuadorian lupinus
[26] observed from different
a significant areas
decrease in
(INIAP-450,
some compounds INIAP-451 andfor
(96.83% criollo),
phenolswith
andan49.42%
antioxidant capacity ofduring
for carotenoids) 18.88, 37.07 and 29.27
debittering and
µfermentation. In this sense,
g Trolox/g debittered Córdova-Ramos,
sample, et al. [109],
respectively, which are in observed
the rangeaof 50%
thatloss of phenol
obtained in
content
tarwi in (Figure
flour Andean6B).lupine (genotipes Altagracia, Andenes and Yunguyo) with debittering
and spray drying.

(A)

(B)

Figure6.6.(A)
Figure (A)Total
Totalphenolic
phenoliccontent,
content,and
and(B)
(B)antioxidant
antioxidantactivity
activityby
byABTS
ABTSofofflours.
flours.Different
Differentletters
letters
(a, b, c, d) or (x, y, z, . . . ) indicate significant differences between
(a, b, c, d) or (x, y, z,..) indicate significant differences between samples. samples.

The antioxidant
3.12. Cluster Analysis andactivity (Figure
Principal 6B) seemed
Component not to be related to the phenol content; on
Analysis
the contrary, sometimes an inverse relationship was observed since flours with the lowest
The cluster analysis is represented in the dendrogram in Figure 7A. Taro and achira
phenol content (arracacha and tarwi) showed the highest antioxidant activity (p < 0.05).
flours are in the same cluster, very close to camote flour, and are organized with tarwi in
The lowest antioxidant activity corresponded to mashua flour (p < 0.05), despite the latter
an upper cluster. Oca and arracacha flours form another cluster, joining mashua flour in
showing the highest content of phenols. This may be due to the fact that not only flavonoids
an upper
and otherone. Thesecompounds
phenolic results are contribute
interestingtobecause they allow
the antioxidant us toofspeculate
activity about
these crops, but the
also
degree of similarity among flours and, therefore, about the possibility to substitute
carotenes and vitamin C, which are present in different amounts in these tubers, rhizomes some
flours for others
and grains in the elaboration
[58,59,108]. ABTS assays ofshowed
productsanwhen they areactivity
antioxidant either located in the same
of 114 µg/mL in the
cluster
water extract of achira (Canna indica) rhizomes from Mysore (India), [32]. On thefor
or very close. However, the principal component analysis will allow a better
other hand,
understanding of how similar or different the flours are.
Agronomy 2021, 11, 1693 21 of 28

it was observed that debittering three varieties of tarwi (from Peru) produces a decrease
in ABTS of 52.9%, and the subsequent spray drying produces a further 8% decrease in
ABTS activity [109]. Villacrés, et al. [26] observed a decrease in the antioxidant activity of
96.13% in three varieties of Ecuadorian lupinus from different areas (INIAP-450, INIAP-451
and criollo), with an antioxidant capacity of 18.88, 37.07 and 29.27 µg Trolox/g debittered
sample, respectively, which are in the range of that obtained in tarwi flour (Figure 6B).

3.12. Cluster Analysis and Principal Component Analysis

The cluster analysis is represented in the dendrogram in Figure 7A. Taro and achira
flours are in the same cluster, very close to camote flour, and are organized with tarwi in
an upper cluster. Oca and arracacha flours form another cluster, joining mashua flour in
an upper one. These results are interesting because they allow us to speculate about the
degree of similarity among flours and, therefore, about the possibility to substitute some
flours for others in the elaboration of products when they are either located in the same
Agronomy 2021, 11, x FOR PEER REVIEW
cluster or very close. However, the principal component analysis will allow for 22 of 29
a better
understanding of how similar or different the flours are.

Figure 7.
Figure 7. (A)
(A) Hierarchical
Hierarchical cluster
cluster analysis,
analysis, and
and (B)
(B) principal
principalcomponent
componentanalysis.
analysis.

The principal
The principal component
component analysis
analysis (PCA)
(PCA)yields
yieldsseveral
severalprincipal
principalcomponents
components(PC),(PC),
PC1 and
PC1 and PC2 explain 67.7%
67.7% variance
variance(Table
(Table 7,
7,Figure
Figure7B).
7B).Table
Table77shows,
shows,inincolored
coloredbands,
bands,
the variables
the variables analyzed according
according to
tocomposition,
composition,color,
color,granulometry,
granulometry,gelatinization
gelatinizationtem-
tem-
perature, functional
perature, functional properties,
properties, rheology,
rheology, and
and bioactive
bioactive properties.
properties.PC1
PC1explained
explainedflour
flour
constituents with high correlation,
constituents correlation, such
such as
as moisture
moistureand
andfiber,
fiber,and
andwith
withaalower
lowerloading
loading
such as protein,
such protein,fat,
fat,and
andnon-starch
non-starchcarbohydrate
carbohydratecontents (negative
contents correlation).
(negative PC1 also
correlation). PC1
showed a high loading of the fineness index and bulk index (negative correlation). How-
ever, the average granule size, observed in microscopy, does not seem to have any rele-
vance or loading in any of the PCs. Regarding hydration properties, only solubility
showed a very low loading with negative correlation, which is attributed to the non-starch
Agronomy 2021, 11, 1693 22 of 28

also showed a high loading of the fineness index and bulk index (negative correlation).
However, the average granule size, observed in microscopy, does not seem to have any
relevance or loading in any of the PCs. Regarding hydration properties, only solubility
showed a very low loading with negative correlation, which is attributed to the non-starch
compounds of the flours absorbing water and favoring hydration, as previously described.
Concerning the viscoelastic properties, all of them showed loading in PC1 with a high
and positive correlation, which indicates the importance of fiber and, to a lesser extent, of
protein, in the gelling and viscoelastic behavior of flours. The phenol content showed some
loading in PC1 (negative correlation), but not with the antioxidant activity (ABTS). More-
over, ABTS does not show a correlation with any PC. Weight of the color parameters was
distributed in the different PCs; however, a* showed more loading in PC1, with a negative
correlation, as well as the phenol content. The greater tendency to redness could be linked
to the correlation of the phenol content.

Table 7. Variance, variance cumulative, and factor loading of principal components (PC) for the
variables of flours.

Variables CP 1 CP 2 CP 3 CP 4
Variance (%) 43.4 24.3 13.9 9.2
Cumulative (%) 43.4 67.7 81.6 90.8
Moisture −0.84 −0.41 0.16 −0.05
Protein 0.59 −0.8 −0.06 −0.08
Fat 0.57 −0.8 −0.16 −0.05
Ash 0.07 0.48 0.69 −0.39
Fiber 0.81 0.12 0.24 −0.24
Total CH −0.5 0.85 −0.03 0.14
Starch 0.1 0.96 0.12 −0.24
Amylose −0.43 −0.7 0.51 −0.1
Amylopectin 0.43 0.7 −0.51 0.1
L* 0.55 −0.07 −0.68 −0.45
a* −0.8 0.14 0.36 0.44
b* −0.54 −0.68 0.36 −0.22
C* −0.57 −0.67 0.39 −0.13
H 0.12 −0.53 −0.13 −0.79
WI 0.63 0.3 −0.63 −0.25
Fineness Index 0.75 −0.59 0.09 0.01
Bulk Density −0.82 0.54 −0.05 0.06
Granular Size −0.02 −0.01 0.47 −0.01
Tm −0.01 −0.55 0.02 0.81
FH 0.06 0.53 0.68 −0.44
Solubility −0.54 0.75 0.1 0.23
Water Absorption Capacity −0.49 0.58 0.02 −0.48
n −0.81 0.17 −0.32 0.31
G0 1 0.88 0.06 0.37 0.21
G00 1 0.95 0.11 0.24 0.04
G0 30 0.89 0.16 0.36 0.21
G00 30 0.94 0.17 0.24 0.08
G0 60 0.89 0.18 0.35 0.2
G00 60 0.94 0.19 0.25 0.09
G0 90 0.89 0.19 0.35 0.2
G00 90 0.94 0.2 0.25 0.1
Phenols −0.63 −0.14 0.64 0.04
ABTS 0.42 −0.24 −0.47 0.35
Cophenetic correlation = 0.988

Amylose and amylopectin contents, highly correlated with opposite sign, were ex-
plained in PC2 in which starch showed a greater loading. Protein and fat, also explained
in PC2, have a high negative correlation, as well as non-starch carbohydrates (positive
correlation). The gelatinization temperature (Tm) has a certain negative correlation in this
Agronomy 2021, 11, 1693 23 of 28

PC2 (−0.55), not as markedly as expected owing to the presence of starch and amylopectin,
perhaps due to the existence of non-starch compounds which, as mentioned above, hinder
and delay gelatinization. However, all the hydration properties studied have a positive
weight in PC2, being solubility the highest.
The swelling index is a property of interest to evaluate the state of starch prior to
gelatinization. However, the factor loading is spread between PC2 and PC3. The highest
loading of the swelling index (FH) is in PC 3 with a high positive correlation (Table 7). This
factor explains 13.9% of the variance, in which ash and amylose, amylopectin with inverse
sign, and total phenol content also showed loading. Thus, the role of amylose in swelling
is observed in this component (PC3). It is worth noting that Tm was highly correlated with
PC4, the explained variance being 9.2%, but its correlation was very high, which indicates
that Tm is a very independent factor. This is interesting because there are many studies
that evaluate the behavior of isolated starch, but very few evaluate that of flour, and the
results show the influence of non-starch compounds, and thus the need to study them to
evaluate the effect of the application of these materials in foods.
PCA is represented in its first two PC (Figure 7B). The group for each flour can be
observed marked with the centroid, revealing how achira, camote and taro flours are very
close, indicating that they share a degree of similarity in physico-chemical and functional
properties, mainly in viscoelastic properties, fiber and amylopectin contents. Tarwi flour
seems to be as strongly influenced by viscoelastic properties and fiber as the previous ones
(PC1), however, the legume shows a strong loading of the fineness index (FI), protein and
fat content, markedly in PC2. Arracacha flour is quite different from the aforementioned
flours in PC1, but similar in PC2. Oca flour is even more distant in PC1 and PC2. Mashua
flour is opposite in all the properties to achira, camote and taro flours. The results from
PCA allow us to know the similarities and differences among the characteristics of flours
from different crops in order to formulate new products or use them as ingredients in
existing ones. The knowledge of their physico-chemical characteristics as well as their
techno-functional capacities makes possible their design in a more competitive way and
even mixing these flours, thus enhancing their nutritional and functional capacities.

4. Conclusions
The results of this study provide information on the proximal composition, physico-
chemical and technological properties of underused Andean crop flours from Ecuador.
The proportions of carbohydrates, protein and fiber are the determinants of the nutritional
quality of these flours. In fact, all the flours accomplish the requirements to be labeled as
“high in fiber”, except for oca flour, which can be considered a “source of fiber”. The starch
content of flours was lower than expected; therefore, foods in which Andean crop flour is
incorporated would be of interest for the control of the glycemic index.
The color of flours was located in the area of intense yellow with tones that are slightly
shifted to the orange area, probably due to the effect of Maillard reactions and carameliza-
tion resulting from their production process, although some presented a yellow or orange
coloration characteristic of the crop. Regarding the granulometric analysis, the fineness
modulus characterized the particles of these flours as medium-sized. The structural mor-
phology of the Andean crop flours revealed the integrity of starch granules and the presence
of protein and fiber, more abundant as their concentration was higher. The gelatiniza-
tion temperature of the starch ranged from 68.4 to 81.5 ◦ C, attributed to the presence of
non-starch compounds, which compete with starch for water, and inhibit gelatinization
until higher temperatures are reached. The rheology of doughs developed with Andean
crop flours showed a viscoelastic behavior, although at high angular frequencies, taro
showed a greater fluidity (G00 > G0 ). As with their crops of origin, all flours presented total
phenol contents, especially mashua flour, and in all flours there was evidence of antioxidant
activity. The cluster and PCA allowed establishing the relationship among the properties
and characteristics of flours, in order to determine their role in the new components as
well as similarities and discrepancies, simplifying knowledge for future applications. The
Agronomy 2021, 11, 1693 24 of 28

results of the present study demonstrate that Andean crops, when subjected to a flour
production process, present interesting properties to be used as ingredients in food pro-
duction. Since the compositions and properties of the flours are different, mixing them in
different proportions will allow the formulation of foods with interesting nutritional and
techno-functional properties.

Author Contributions: Conceptualization, D.S. and M.A.; methodology, D.S.; software, D.S. and
M.A.; formal analysis, D.S., M.A., M.E.L.-C. and M.P.M.; investigation, D.S., I.O., M.B., R.R.-M. and
M.A.; resources, D.S., M.A., M.E.L.-C. and M.P.M.; data curation, D.S., M.A., M.E.L.-C. and M.P.M.;
writing—original draft preparation, D.S.; writing—review and editing, M.A., R.R.-M., M.E.L.-C. and
M.P.M.; visualization, D.S., M.E.L.-C. and M.P.M.; supervision, M.A., M.E.L.-C. and M.P.M.; project
administration, M.A., M.E.L.-C. and M.P.M.; funding acquisition, M.A., M.E.L.-C. and M.P.M. All
authors have read and agreed to the published version of the manuscript.
Funding: This research was funded by Dirección de Investigación y Desarrollo (DIDE) and the
Universidad Técnica de Ambato-Ecuador project PFCIAL-031-DS, the Inédita Project 20190015 funded
by Secretaría Nacional de Educación Superior, Ciencia y Tecnología-Ecuador (SENESCYT), and the
NANOALIVAL project AGL2017-84161 funded by MICINNIN, SPAIN and European Regional
Development Fund (FEDER) and project 202070E218 funded by CSIC, SPAIN.
Acknowledgments: The authors would like to thank the organizations that have made possible the
development of this work through the funding of the following projects: PFCIAL-031-DS Project
“Development of a prototype of a gluten-free farinaceous mixture for confectionery, using under-
utilized traditional Andean crops, funded by the Dirección de Investigación y Desarrollo (DIDE)
and the Universidad Técnica de Ambato-Ecuador (resolution 0193-CU-P-2018), the Inédita Project
20190015 “Development of wheat and gluten-free food products from underused Andean crops and
agro-industrial waste”, funded Secretaría Nacional de Educación Superior, Ciencia y Tecnología-
Ecuador (SENESCYT). Unpublished Project 20190015. 02/05/2019-02/08/2020.NANOALIVAL
project AGL2017-84161 funded by MICINNIN, SPAIN and European Regional Development Fund
(FEDER) and project 202070E218 funded by CSIC, SPAIN.
Conflicts of Interest: The authors declare no conflict of interest.

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